The effects of humidity on tin whisker growth by immersion tin plating and tin solder dipping surface finishes

The drive to replace lead (Pb) from electronics has led to the replacement of tin (Sn) alloys as the terminal plating for electronic devices. However, the deposition of Sn based alloys as the component surface finish tends to induce Sn whisker that causes unintended electric shorts when the conductive whiskers grow across to the adjacent conductor. Internal stress is considered as the driving force that causes the growth of Sn whiskers. In this study, stress type of elevated temperature/ humidity exposure at 55C/85%RH with the storage for up to 24 months was conducted to define the acceleration factor in samples with deposition of immersion Sn plating and Sn solder dipping. The addition of Nickel (Ni) under-layer was also applied to examine the correlation to field conditions. The results showed that the whisker length increased in high humidity irrespective of the deposition methods. It was also shown that pure Sn solder dipping mitigated the whisker growth but does not completely prevent it when alloying Sn with 0.4%wtCu. Additionally, Ni under-layer was indicated to be more efficient in mitigating the growth of whisker by prolonging the incubation time for whisker formation.

RF magnetron sputtering deposition of bioactive Ca-P-based coatings on Ti-6Al-4V alloy

RF magnetron concurrent sputtering of Hydroxyapatite and Ti forming functionally graded calcium phosphate-based composite bioactive films on Ti-6Al-4V orthopedic alloy is reported. Calcium oxide phosphate (4CaO•P2O5) is the main crystalline phase. In vitro cell culturing tests suggest outstanding biocompatibility of the Ca-P-Ti films. Images of the plasma-enhanced sputtering processes and cell culturing are presented and discussed.

Stoichiometry, crystallinity, and nano-scale surface morphology of the graded calcium phosphate-based bio-ceramic interlayer on Ti-Al-V

A plasma-assisted concurrent Rf sputtering technique for fabrication of biocompatible, functionally graded CaP-based interlayer on Ti-6Al-4V orthopedic alloy is reported. Each layer in the coating is designed to meet a specific functionality. The adherent to the metal layer features elevated content of Ti and supports excellent ceramic-metal interfacial stability. The middle layer features nanocrystalline structure and mimics natural bone apatites. The technique allows one to reproduce Ca/P ratios intrinsic to major natural calcium phosphates. Surface morphology of the outer, a few to few tens of nanometers thick, layer, has been tailored to fit the requirements for the bio-molecule/protein attachment factors. Various material and surface characterization techniques confirm that the optimal surface morphology of the outer layer is achieved for the process conditions yielding nanocrystalline structure of the middle layer. Preliminary cell culturing tests confirm the link between the tailored nano-scale surface morphology, parameters of the middle nanostructured layer, and overall biocompatibility of the coating.

Porous polyurethane coatings bonded onto surface-modified titanium substrates for the growth of an endothelial cell layer

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.

Synthesis of one-dimensional nanocomposites based on alumina nanofibres and their catalytic applications

Materials with one-dimensional (1D) nanostructure are important for catalysis. They are the preferred building blocks for catalytic nanoarchitecture, and can be used to fabricate designer catalysts. In this thesis, one such material, alumina nanofibre, was used as a precursor to prepare a range of nanocomposite catalysts. Utilising the specific properties of alumina nanofibres, a novel approach was developed to prepare macro-mesoporous nanocomposites, which consist of a stacked, fibrous nanocomposite with a core-shell structure. Two kinds of fibrous ZrO2/Al2O3 and TiO2/Al2O3 nanocomposites were successfully synthesised using boehmite nanofibers as a hard temperate and followed by a simple calcination. The alumina nanofibres provide the resultant nanocomposites with good thermal stability and mechanical stability. A series of one-dimensional (1D) zirconia/alumina nanocomposites were prepared by the deposition of zirconium species onto the 3D framework of boehmite nanofibres formed by dispersing boehmite nanofibres into a butanol solution, followed by calcination at 773 K. The materials were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and Fourier Transform Infrared spectroscopy (FT-IR). The results demonstrated that when the molar percentage, X, X=100*Zr/(Al+Zr), was > 30%, extremely long ZrO2/Al2O3 composite nanorods with evenly distributed ZrO2 nanocrystals formed on their surface. The stacking of such nanorods gave rise to a new kind of macroporous material without the use of any organic space filler\template or other specific drying techniques. The mechanism for the formation of these long ZrO2/Al2O3 composite nanorods is proposed in this work. A series of solid-superacid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid superacid counterparts were characterised by a variety of techniques including 27Al MAS-NMR, SEM, TEM, XPS, Nitrogen adsorption and Infrared Emission Spectroscopy. NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained superacids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia. Preparation of hierarchically macro-mesoporous catalyst by loading nanocrystallites on the framework of alumina bundles can provide an alternative system to design advanced nanocomposite catalyst with enhanced performance. A series of macro-mesoporous TiO2/Al2O3 nanocomposites with different morphologies were synthesised. The materials were calcined at 723 K and were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and UV-visible spectroscopy (UV-visible). A modified approach was proposed for the synthesis of 1D (fibrous) nanocomposite with higher Ti/Al molar ratio (2:1) at lower temperature (<100oC), which makes it possible to synthesize such materials on industrial scale. The performances of a series of resultant TiO2/Al2O3 nanocomposites with different morphologies were evaluated as a photocatalyst for the phenol degradation under UV irradiation. The photocatalyst (Ti/Al =2) with fibrous morphology exhibits higher activity than that of the photocatalyst with microspherical morphology which indeed has the highest Ti to Al molar ratio (Ti/Al =3) in the series of as-synthesised hierarchical TiO2/Al2O3 nanocomposites. Furthermore, the photocatalytic performances, for the fibrous nanocomposites with Ti/Al=2, were optimized by calcination at elevated temperatures. The nanocomposite prepared by calcination at 750oC exhibits the highest catalytic activity, and its performance per TiO2 unit is very close to that of the gold standard, Degussa P 25. This work also emphasizes two advantages of the nanocomposites with fibrous morphology: (1) the resistance to sintering, and (2) good catalyst recovery.

Studies on bending limitations for the optimal fit of orthopaedic bone plates

Distal tibial fractures are now commonly treated via intermedullary plate fixation due to higher rates of union and lower rates of postoperative complications. However, patient specific bone morphology demands manual deformation of the plate to ensure appropriate fit along the bone Distal tibial fractures are now commonly treated via intermedullary plate fixation due to higher rates of union and lower rates of postoperative complications. However, patient specific bone morphology demands manual deformation of the plate to ensure appropriate fit along the bone contours, and depending on the material of the plate, different outcomes have been reported along with postoperative complications. A comparative analysis of Stainless Steel 316L and Ti-6Al-4V alloys was carried to estimate the safe bending limit for appropriate fits. The results from the ANSYS FEA simulations were validated with experiments based on ASTM F382-99. It is found that SS316L is better suited for large deformations (up to 16˚ in proximal tip and 7.5˚ in distal end) and Ti for smaller deformation contours (up to 3˚ in proximal tip and 1.8˚ in distal end). The results of this study have profound implications for the choice of plates based on preliminary radiographical fracture examinations to ensure better fixation and higher rates of union of distal tibial fractures.

TiltZoom : tilt-based zooming control for easy one-handed mobile interactions

In this paper, we present TiltZoom, a collection of tilt-based interaction techniques designed for easy one-handed zooming on mobile devices. TiltZoom represents novel gestural interaction techniques, implemented using rate-of-rotation readings from a gyroscope, a sensor commonly embedded on current generation smart phones. We designed and experimented three variants of TiltZoom - Tilt Level, Tilt and Hold and Flip Gesture. The design decisions for all three variants are discussed in this paper and their performance, as well as subjective user experience are evaluated and compared against conventional touch-based zooming techniques. TiltZoom appears to be a worthy addition to current established collection of gesture-based mobile interaction techniques for zooming controls, especially when user has only one hand available when moving about.

Pt/anodized TiO2/SiC-based MOS device for hydrocarbon sensing

Pt/anodized TiO2/SiC based metal-oxide-semiconductor (MOS) devices were fabricated and characterized for their sensitivity towards propene (C3H6). Titanium (Ti) thin films were deposited onto the SiC substrates using a filtered cathodic vacuum arc (FCVA) method. Fluoride ions containing neutral electrolyte (0.5 wt% NH4F in ethylene glycol)were used to anodize the Ti films. The anodized films were subsequently annealed at 600 °C for 4 hrs in an oxygen rich environment to obtain TiO2. The current-voltage(I-V) characteristics of the Pt/TiO2/SiC devices were measured in different concentrations of propene. Exposure to the analyte gas caused a change in the Schottky barrier height and hence a lateral shift in the I-V characteristics. The effective change in the barrier height for 1% propene was calculated as 32.8 meV at 620°C. The dynamic response of the sensors was also investigated and a voltage shift of 157 mV was measured at 620°C during exposure to 1% propene.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

pGreen : a versatile and flexible binary Ti vector for Agrobacterium-mediated plant transformation

Binary Ti vectors are the plasmid vectors of choice in Agrobacterium-mediated plant transformation protocols. The pGreen series of binary Ti vectors are configured for ease-of-use and to meet the demands of a wide range of transformation procedures for many plant species. This plasmid system allows any arrangement of selectable marker and reporter gene at the right and left T-DNA borders without compromising the choice of restriction sites for cloning, since the pGreen cloning sites are based on the well-known pBluescript general vector plasmids. Its size and copy number in Escherichia coli offers increased efficiencies in routine in vitro recombination procedures. pGreen can replicate in Agrobacterium only if another plasmid, pSoup, is co-resident in the same strain. pSoup provides replication functions in trans for pGreen. The removal of RepA and Mob functions has enabled the size of pGreen to be kept to a minimum. Versions of pGreen have been used to transform several plant species with the same efficiencies as other binary Ti vectors. Information on the pGreen plasmid system is supplemented by an Internet site (http://www.pgreen.ac.uk) through which comprehensive information, protocols, order forms and lists of different pGreen marker gene permutations can be found.

A guide to Agrobacterium binary Ti vectors

Agrobacterium-based plasmid vectors allow the transformation of a wide range of plant species by capitalizing on a natural bacterial system to introduce DNA into the nuclear genome of plants. It is often a complex task to consider fully all the possible plasmid vectors and Agrobacterium strains available, and it can thus be difficult to take full advantage of these research tools. This practical guide is a survey of the many binary Ti plasmid vectors and Agrobacterium strains available, and aims to help researchers to make an informed decision about the system that is best suited to their needs...

Surface chemistry, dispersion behavior, and slip casting of Ti 3AlC2 suspensions

The surface chemistry and dispersion properties of aqueous Ti 3AlC2 suspension were studied in terms of hydrolysis, adsorption, electrokinetic, and rheological measurements. The Ti 3AlC2 particle had complex surface hydroxyl groups, such as ≡Ti-OH,=Al-OH, and -OTi-(OH)2, etc. The surface charging of the Ti3AlC2 particle and the ion environment of suspensions were governed by these surface groups, which thus strongly influenced the stability of Ti3AlC2 suspensions. PAA dispersant was added into the Ti3AlC2 suspension to depress the hydrolysis of the surface groups by the adsorption protection mechanism and to increase the stability of the suspension by the steric effect. Ti3AlC2 suspensions with 2.0 dwb% PAA had an excellent stability at pH=∼5 and presented the characteristics of Newtonian fluid. Based on the well-dispersed suspension, dense Ti3AlC2 materials were obtained by slip casting and after pressureless sintering. This work provides a feasible forming method for the engineering applications of MAX-phase ceramics, wherein complex shapes, large dimensions, or controlled microstructures are needed.