953 resultados para chemical technology


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Industrial applications of the simulated-moving-bed (SMB) chromatographic technology have brought an emergent demand to improve the SMB process operation for higher efficiency and better robustness. Improved process modelling and more-efficient model computation will pave a path to meet this demand. However, the SMB unit operation exhibits complex dynamics, leading to challenges in SMB process modelling and model computation. One of the significant problems is how to quickly obtain the steady state of an SMB process model, as process metrics at the steady state are critical for process design and real-time control. The conventional computation method, which solves the process model cycle by cycle and takes the solution only when a cyclic steady state is reached after a certain number of switching, is computationally expensive. Adopting the concept of quasi-envelope (QE), this work treats the SMB operation as a pseudo-oscillatory process because of its large number of continuous switching. Then, an innovative QE computation scheme is developed to quickly obtain the steady state solution of an SMB model for any arbitrary initial condition. The QE computation scheme allows larger steps to be taken for predicting the slow change of the starting state within each switching. Incorporating with the wavelet-based technique, this scheme is demonstrated to be effective and efficient for an SMB sugar separation process. Moreover, investigations are also carried out on when the computation scheme should be activated and how the convergence of the scheme is affected by a variable stepsize.

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The unusual (1:1) complex ‘adduct’ salt of copper(II) with 4,5-dichlorophthalic acid (H2DCPA), having formula [Cu(H2O)4(C8H3Cl2O4) (C8H4Cl2O4)] . (C8H3Cl2O4) has been synthesized and characterized using single-crystal X-ray diffraction. Crystals are monoclinic, space group P21/c, with Z = 4 in a cell with dimensions a = 20.1376(7), b =12.8408(4) c = 12.1910(4) Å, β = 105.509(4)o. The complex is based on discrete tetragonally distorted octahedral [CuO6] coordination centres with the four water ligands occupying the square planar sites [Cu-O, 1.962(4)-1.987(4) Å] and the monodentate carboxyl-O donors of two DCPA ligand species in the axial sites. The first of these bonds [Cu-O, 2.341(4) Å] is with an oxygen of a HDCPA monoanion, the second with an oxygen of a H2DCPA acid species [Cu-O, 2.418(4) Å]. The un-coordinated ‘adduct’ molecule is a HDCPA counter anion which is strongly hydrogen-bonded to the coordinated H2DCPA ligand [O… O, 2.503(6) Å] while a number of peripheral intra- and intermolecular hydrogen-bonding interactions give a two-dimensional network structure.

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This chapter explores youth media production involving video games within a formal media education context. It investigates the possibilities for agency in student production contexts where emphasis is on the acquisition of technological skills. It explores alternatives to the well-established approach to media education that aims to develop students’ critical reading capacities as a means to agency. The chapter discusses some of the implications of the differences between youth production with ‘older’ technologies like video and new forms like multimedia production. It also discusses theories of agency as they relate to media education and the challenges of considering agency in relation to new media production. Post structuralist concepts are introduced and used as the basis to explore opportunities for agency in the context of students designing and producing aspects of video games. The chapter argues that the creative and experimental work students undertake while using software to make games artefacts opens up possibilities for agency.

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Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm−1 (ν1-band), 15,230–14,740 cm−1 (ν2-band) and 9,200–9,145 cm−1 (ν3-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) → 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν1- and ν3-bands and non-Gaussian shape of ν3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.

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Natural iowaite, magnesium–ferric oxychloride mineral having light green color originating from Australia has been characterized by EPR, optical, IR, and Raman spectroscopy. The optical spectrum exhibits a number of electronic bands due to both Fe(III) and Mn(II) ions in iowaite. From EPR studies, the g values are calculated for Fe(III) and g and A values for Mn(II). EPR and optical absorption studies confirm that Fe(III) and Mn(II) are in distorted octahedral geometry. The bands that appear both in NIR and Raman spectra are due to the overtones and combinations of water and carbonate molecules. Thus EPR, optical, and Raman spectroscopy have proven most useful for the study of the chemistry of natural iowaite and chemical changes in the mineral.

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The crystal structures of the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine, viz. diisopropylaminium 2-carboxy-4,5-dichlorobenzoate (1) and hexamethylenetetraminium 2-carboxy-4,5-dichlorobenzoate hemihydrate (2), have been determined. Crystals of both 1 and 2 are triclinic, space group P-1, with Z = 2 in cells with a = 7.0299(5), b = 9.4712(7), c = 12.790(1)Å, α = 99.476(6), β = 100.843(6), γ = 97.578(6)o (1) and a = 7.5624(8), b = 9.8918(8), c = 11.5881(16)Å, α = 65.660(6), β = 86.583(4), γ = 86.987(8)o (2). In each, one-dimensional hydrogen-bonded chain structures are found: in 1 formed through aminium N+-H...Ocarboxyl cation-anion interactions. In 2, the chains are formed through anion carboxyl O...H-Obridging water interactions with the cations peripherally bound. In both structures, the hydrogen phthalate anions are essentially planar with short intra-species carboxylic acid O-H...Ocarboxyl hydrogen bonds [O…O, 2.381(3) Å (1) and 2.381(8) Å (2)].

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The crystal structure of the modified unsymmetrically N, N'-substituted viologen chromophore, N-ethyl- N'-(2-phosphonoethyl)-4, 4'-bipyridinium dichloride 0.75 hydrate. (1) has been determined. Crystals are triclinic, space group P-1 with Z = 2 in a cell with a = 7.2550(1), b = 13.2038(5), c = 18.5752(7) Å, α = 86.495(3), β = 83.527(2), γ = 88.921(2)o. The two independent but pseudo-symmetrically related cations in the asymmetric unit form one-dimensional hydrogen-bonded chains through short homomeric phosphonic acid O-H...O links [2.455(4), 2.464(4)A] while two of the chloride anions are similarly strongly linked to phosphonic acid groups [O-H…Cl, 2.889(4), 2.896(4)Å]. The other two chloride anions together with the two water molecules of solvation (one with partial occupancy) form unusual cyclic hydrogen-bonded bis(Cl...water) dianion units which lie between the layers of bipyridylium rings of the cation chain structures with which they are weakly associated.

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This study explores strategic decision-making (SDM) in micro-firms, an economically significant business subsector. As extant large- and small-firm literature currently proffers an incomplete characterization of SDM in very small enterprises, a multiple-case methodology was used to investigate how these firms make strategic decisions. Eleven Australian Information Technology service micro-firms participated in the study. Using an information-processing lens, the study uncovered patterns of SDM in micro-firms and derived a theoretical micro-firm SDM model. This research also identifies several implications for micro-firm management and directions for future research, contributing to the understanding of micro-firm SDM in both theory and practice.

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The impact of technology on the health and well-being of workers has been a topic of interest since computers and computerized technology were widely introduced in the 1980s. Of recent concern is the impact of rapid technological advances on individuals’ psychological well-being, especially due to advancements in mobile technology which have increased many workers’ accessibility and expected productivity. In this chapter we focus on the associations between occupational stress and technology, especially behavioral and psychological reactions. We discuss some key facilitators and barriers associated with users’ acceptance of and engagement with information and communication technology. We conclude with recommendations for ongoing research on managing occupational health and well-being in conjunction with technological advancements.

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Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

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The thermal analysis of euchroite shows two mass loss steps in the temperature range 100 to 105°C and 185 to 205°C. These mass loss steps are attributed to dehydration and dehydroxylation of the mineral. Hot stage Raman spectroscopy (HSRS) has been used to study the thermal stability of the mineral euchroite, a mineral involved in a complex set of equilibria between the copper hydroxy arsenates: euchroite Cu2(AsO4)(OH).3H2O → olivenite Cu2(AsO4)(OH) → strashimirite Cu8(AsO4)4(OH)4.5H2O → arhbarite Cu2Mg(AsO4)(OH)3. Hot stage Raman spectroscopy inolves the collection of Raman spectra as a function of the temperature. HSRS shows that the mineral euchroite decomposes between 125 and 175 °C with the loss of water. At 125 °C, Raman bands are observed at 858 cm-1 assigned to the ν1 AsO43- symmetric stretching vibration and 801, 822 and 871 cm-1 assigned to the ν3 AsO43- (A1) antisymmetric stretching vibration. A distinct band shift is observed upon heating to 275 °C. At 275 °C the four Raman bands are resolved at 762, 810, 837 and 862 cm-1. Further heating results in the diminution of the intensity in the Raman spectra and this is attributed to sublimation of the arsenate mineral. Hot stage Raman spectroscopy is most useful technique for studying the thermal stability of minerals especially when only very small amounts of mineral are available.

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The transition of cubic indium hydroxide to cubic indium oxide has been studied by thermogravimetric analysis complimented with hot stage Raman spectroscopy. Thermal analysis shows the transition of In(OH)3 to In2O3 occurs at 219°C. The structure and morphology of In(OH)3 synthesised using a soft chemical route at low temperatures was confirmed by X-ray diffraction and scanning electron microscopy. A topotactical relationship exists between the micro/nano-cubes of In(OH)3 and In2O3. The Raman spectrum of In(OH)3 is characterised by an intense sharp band at 309 cm-1 attributed to ν1 In-O symmetric stretching mode, bands at 1137 and 1155 cm-1 attributed to In-OH δ deformation modes, bands at 3083, 3215, 3123 and 3262 cm-1 assigned to the OH stretching vibrations. Upon thermal treatment of In(OH)3 new Raman bands are observed at 125, 295, 488 and 615 cm-1 attributed to In2O3. Changes in the structure of In(OH)3 with thermal treatment is readily followed by hot stage Raman spectroscopy.

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Bayer hydrotalcites prepared using the seawater neutralisation (SWN) process of Bayer liquors are characterised using X-ray diffraction and thermal analysis techniques. The Bayer hydrotalcites are synthesised at four different temperatures (0, 25, 55, 75 °C) to determine the effect on the thermal stability of the hydrotalcite structure, and to identify other precipitates that form at these temperatures. The interlayer distance increased with increasing synthesis temperature, up to 55 °C, and then decreased by 0.14 Å for Bayer hydrotalcites prepared at 75 °C. The three mineralogical phases identified in this investigation are; 1) Bayer hydrotalcite, 2), calcium carbonate species, and 3) hydromagnesite. The DTG curve can be separated into four decomposition steps; 1) the removal of adsorbed water and free interlayer water in hydrotalcite (30 – 230 °C), 2) the dehydroxylation of hydrotalcite and the decarbonation of hydrotalcite (250 – 400 °C), 3) the decarbonation of hydromagnesite (400 – 550 °C), and 4) the decarbonation of aragonite (550 – 650 °C).

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The mineral reevesite and the cobalt substituted reevesite have been synthesised. The d(003) spacings of the minerals ranged from 7.54 to 7.95 Å. The maximum d(003) value occurred at around Ni:Co 0.4:0.6. This maximum in interlayer distance is proposed to be due to a greater number of carbonate anions and water molecules intercalated into the structure. The stability of the reevesite and cobalt doped reevesite was determined by thermogravimetric analysis. The maximum temperature of the reevesite occurs for the unsubstituted reevesite and is around 220°C. The effect of cobalt substitution results in a decrease in thermal stability of the reevesites. Four thermal decomposition steps are observed and are attributed to dehydration, dehydroxylation and decarbonation, decomposition of the formed carbonate and oxygen loss at ~807 °C. A mechanism for the thermal decomposition of the reevesite and the cobalt substituted reevesite is proposed.

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Cardiovascular diseases refer to the class of diseases that involve the heart or blood vessels (arteries and veins). Examples of medical devices for treating the cardiovascular diseases include ventricular assist devices (VADs), artificial heart valves and stents. Metallic biomaterials such as titanium and its alloy are commonly used for ventricular assist devices. However, titanium and its alloy show unacceptable thrombosis, which represents a major obstacle to be overcome. Polyurethane (PU) polymer has better blood compatibility and has been used widely in cardiovascular devices. Thus one aim of the project was to coat a PU polymer onto a titanium substrate by increasing the surface roughness, and surface functionality. Since the endothelium of a blood vessel has the most ideal non-thrombogenic properties, it was the target of this research project to grow an endothelial cell layer as a biological coating based on the tissue engineering strategy. However, seeding endothelial cells on the smooth PU coating surfaces is problematic due to the quick loss of seeded cells which do not adhere to the PU surface. Thus it was another aim of the project to create a porous PU top layer on the dense PU pre-layer-coated titanium substrate. The method of preparing the porous PU layer was based on the solvent casting/particulate leaching (SCPL) modified with centrifugation. Without the step of centrifugation, the distribution of the salt particles was not uniform within the polymer solution, and the degree of interconnection between the salt particles was not well controlled. Using the centrifugal treatment, the pore distribution became uniform and the pore interconnectivity was improved even at a high polymer solution concentration (20%) as the maximal salt weight was added in the polymer solution. The titanium surfaces were modified by alkli and heat treatment, followed by functionlisation using hydrogen peroxide. A silane coupling agent was coated before the application of the dense PU pre-layer and the porous PU top layer. The ability of the porous top layer to grow and retain the endothelial cells was also assessed through cell culture techniques. The bonding strengths of the PU coatings to the modified titanium substrates were measured and related to the surface morphologies. The outcome of the project is that it has laid a foundation to achieve the strategy of endothelialisation for the blood compatibility of medical devices. This thesis is divided into seven chapters. Chapter 2 describes the current state of the art in the field of surface modification in cardiovascular devices such as ventricular assist devices (VADs). It also analyses the pros and cons of the existing coatings, particularly in the context of this research. The surface coatings for VADs have evolved from early organic/ inorganic (passive) coatings, to bioactive coatings (e.g. biomolecules), and to cell-based coatings. Based on the commercial applications and the potential of the coatings, the relevant review is focused on the following six types of coatings: (1) titanium nitride (TiN) coatings, (2) diamond-like carbon (DLC) coatings, (3) 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer coatings, (4) heparin coatings, (5) textured surfaces, and (6) endothelial cell lining. Chapter 3 reviews the polymer scaffolds and one relevant fabrication method. In tissue engineering, the function of a polymeric material is to provide a 3-dimensional architecture (scaffold) which is typically used to accommodate transplanted cells and to guide their growth and the regeneration of tissue. The success of these systems is dependent on the design of the tissue engineering scaffolds. Chapter 4 describes chemical surface treatments for titanium and titanium alloys to increase the bond strength to polymer by altering the substrate surface, for example, by increasing surface roughness or changing surface chemistry. The nature of the surface treatment prior to bonding is found to be a major factor controlling the bonding strength. By increasing surface roughness, an increase in surface area occurs, which allows the adhesive to flow in and around the irregularities on the surface to form a mechanical bond. Changing surface chemistry also results in the formation of a chemical bond. Chapter 5 shows that bond strengths between titanium and polyurethane could be significantly improved by surface treating the titanium prior to bonding. Alkaline heat treatment and H2O2 treatment were applied to change the surface roughness and the surface chemistry of titanium. Surface treatment increases the bond strength by altering the substrate surface in a number of ways, including increasing the surface roughness and changing the surface chemistry. Chapter 6 deals with the characterization of the polyurethane scaffolds, which were fabricated using an enhanced solvent casting/particulate (salt) leaching (SCPL) method developed for preparing three-dimensional porous scaffolds for cardiac tissue engineering. The enhanced method involves the combination of a conventional SCPL method and a step of centrifugation, with the centrifugation being employed to improve the pore uniformity and interconnectivity of the scaffolds. It is shown that the enhanced SCPL method and a collagen coating resulted in a spatially uniform distribution of cells throughout the collagen-coated PU scaffolds.In Chapter 7, the enhanced SCPL method is used to form porous features on the polyurethane-coated titanium substrate. The cavities anchored the endothelial cells to remain on the blood contacting surfaces. It is shown that the surface porosities created by the enhanced SCPL may be useful in forming a stable endothelial layer upon the blood contacting surface. Chapter 8 finally summarises the entire work performed on the fabrication and analysis of the polymer-Ti bonding, the enhanced SCPL method and the PU microporous surface on the metallic substrate. It then outlines the possibilities for future work and research in this area.