The focus of this dissertation is on the development of a solid freeform fabrication (SFF) process for the design and manufacture of porous biodegradable orthopaedic implants from calcium polyphosphate (CPP). Porous CPP structures are used as bone substitutes for regenerating bone defects and/or as substrates in formation of so-called “biphasic” implants for repair of damaged osteochondral tissues. The CPP implants can be utilized in the treatment of many musculoskeletal diseases, osteochondral defects, and bone tumours while replacement of the defect site is required. In this study, the fabrication of CPP structures was developed through a powder-based SFF technique known as adhesive bonding 3D-printing. SFF is an advanced alternative to the “conventional” fabrication method consisting of gravity sintering of CPP pre-forms followed by machining to final form, as SFF enables rapid manufacturing of complex-shaped bio-structures with controlled internal architecture. To address the physical and structural properties of the porous SFF-made components, they were characterized using scanning electron microscopy, micro-CT scanning and mercury intrusion porosimetry. Specific surface area and permeability of the porous structures were also determined. Additionally, the chemical properties (crystallinity) of the specimens were identified by X-ray diffraction. The mechanical properties of the crystalline CPP material were also measured by micro- and nano-indentation. Moreover, the porous structures were tested by uniaxial and diametral mechanical compression to determine the compressive and tensile strengths, respectively. Furthermore, the effect of the stacked-layer orientation on the mechanical properties of the SFF-made constructs was investigated through the production of samples with horizontal or vertical stacked-layers. The properties of the SFF-made samples were compared with those of the conventionally-made CPP constructs. The SFF-made implants showed drastically higher compressive mechanical strength compared to the conventionally-formed samples with identical porosity. It was also shown that the orientation of the stacked-layer has substantial influence on the mechanical strengths. Moreover, this thesis examined the ability of in vitro forming of cartilaginous tissue on the SFF-made substrates where the chondrocytes cellular response to the CPP implants was evaluated histologically and biochemically. In addition, an initial in vivo assessment of the CPP structures as bone substitutes was conducted using a rabbit medial femoral site model. Significant amount of new-bone was formed within the CPP porous constructs during the 6-week implantation period demonstrating appropriate biological response of SFF-made CPP structures for bone substitute applications. Another accomplishment of this thesis was the development of a mathematical model which predicts the compact density of powder layers spread by a counter-rotating roller in the SFF technique. The results may be used in the control of the apparent density of the final implant. The potential of the developed SFF method as an efficient and reproducible technique for the production of porous CPP structures for use in orthopaedics and musculoskeletal tissue regenerative applications was concluded.

Brackish springs are relatively frequent phenomena in coastal carbonate formations and their existence has been extensively reported in Mediterranean coasts. In fact, more than 300 brackish springs have been identified only in the coast of the former Yugoslavia. They essentially consist of inland or submarine karst outlets discharging waters with flow-dependent salinity. The phenomenon is particularly surprising in inland springs, where high flow rates with significant salinities (presumably coming from the sea) may be discharged several meters above sea level. In addition to its scientific interest, brackish springs hold a strategic potential as a source of water in areas with often limited water resources. In order to design their appropriate management a quantitative understanding of their controlling mechanisms both in general and at every particular spring has to be achieved.These mechanisms have been studied for many years but some controversy still remains. It is clear that they are related to deep well developed karst systems. Under these conditions, groundwater flows in a turbulent mode through a network of interconnected conduits immersed in a porous matrix with slow Darcyan flow velocities. Surprisingly, different models to explain the functioning of the system, although based on different conceptual and methodological approaches lead to similar results. This sugests that a global study on the salinitzation mechanisms of brackish springs should be undertaken. Here, we first derive the equations governing turbulent flow for density-dependent fluids and describe different mechanisms of salinization of inland brackish springs, in order to compare with the spring discharge and concentration response for those mechanisms of salinization.The insights gained in this analysis are applied to the study of S'Almadrava spring (Mallorca, Spain). This spring discharges up to 2 m3/s with salinities of 20 mS/cm at an elevation of 8 m.a.s.l. It generally displays an inverse relation between discharge rate and concentration (i.e., discharging higher salinity waters for low flow rates, and vice versa). A hypothetical but geologically feasible dual permeability model is proposed to reproduce observed salinity variations for both the dry and wet seasons but also to explain the secondary salinity peaks observed after every rainfall event. Model results agree with observations, but the lack of geological information at depth impedes model validation. Therefore, a second validation of the conceptual model is undertaken based on high-frequency geochemical observations. Due to the highly dynamic conditions of the system, the geochemical data was analyzed using fully coupled reactive transport modelling. The interpretation of geochemical data not only helps on validating conceptual models but also yields information on the water-rock interaction processes occurring at deep carbonate systems. In fact, one of the processes initially proposed to explain the occurrence of well-developed karst systems at depth, is the enlargement of tectonic fissures by carbonate dissolution due to the mixing of fresh and seawater.The theory of dissolution by mixing waters is based on the fact that when two solutions are mixed, concentrations in the mixture are volume weighted averages of the two end-members, but the thermodynamic activities of the species controlling the water-mineral reactions are non linear functions of the mixing ratio. Therefore, two end-member solutions in equilibrium with a solid phase could lead to an undersaturated mixture depending on several factors, most notably CO2 content and ionic strength. Observation of mixing and carbonate dissolution at depth has not been possible because of technical difficulties. More accessible to observation is the seawater mixing zone in coastal aquifers where calcite undersaturation and/or calcite dissolution have been reported numerous times. Yet, dissolution in coastal environments is not always clear and oversaturation or lack of dissolution in mixing zones have also been described. This apparent inconsistency on field observations around the world prompted the studies of the second part of the thesis. Flow-through laboratory experiments were performed in CO2-controlled atmosphere in order to quantify the dependence of the dissolution of calcite with the mixing ratio, and the role that CO2 variations may have on enhancing the dissolution capacity of the mixture. Results show that, although dissolution occurs, the major carbonate dissolution in aquifers must be considered only in a geological time scale. Sanford and Konikow (1989) predicted the location and magnitude of long term porosity development of coastal aquifers, based on a two step method. We compare their results with a reactive transport model approach in 1D and 2D, showing that reactive transport is required to properly understand the phenomenon because it is found that dissolution is controlled not only by geochemical factors but also by the rate at which fresh and salt water mix (i.e., by dispersion).

The incorporation of porosity in a material potentially results in the changes in electrical, mechanical and electrical properties and has generated much interest by researchers. The development of new techniques for inducing porosity in thin films may prove advantageous if they lead to a decrease in processing complexity, or an increase in the processing flexibility by widening the window of compatible physical conditions, or the improvement of the final properties of the porous materials. Two processing techniques were developed to produce porosity in thin dielectric films at temperatures below the glass transition temperature of the host matrix. These glassy-regime processing methods relied on the susceptibility of hydrogen silsesquioxane (HSQ) to gelation in the glassy regime when exposed to polar substances. Both of these glassy-regime processing methods relied on the susceptibility of hydrogen silsesquioxane (HSQ) towards gelation in the glassy regime when exposed to polar substances. The first processing method made use of co-solvent mixtures of polar non-protic organic solvent to serve both as gelation catalysts and pore-generators. HSQ films were soaked in the polar organic co-solvents, which penetrated the films and initiated crosslinking throughout the matrix. Afterwards the films were baked, volatilizing entrapped solvents and producing air pockets within the rigid matrix. The second porosity method used UV-radiation to initiate acid-catalyzed decomposition of polycarbonate sacrificial polymers after first using bases to catalyze the gelation of HSQ. The radiation-based (direct-write) decomposition of the porogen enabled the selective patterning of regions porosity via the use of a photomask, which resulted in the creation of refractive index profiles in the direct-written films. Porous films that were produced by these two glassy-state processing techniques were used to build slab waveguide structures. Optical characterization experiments showed that the fabricated waveguides had average propagation losses of 16 - 27 dB/cm for the first guided TE mode and about 36-40 dB/cm, for the second TE guided mode. It is believed that the large propagation loss values were caused by a combination of the Rayleigh scattering from the relatively large UV-induced pores produced in the direct-write layers as well as scattering induced by surface roughness.

<p>Zr-based materials have found their main application in the nuclear field having high corrosion resistance and low neutron absorption cross-section. The oxide layer that is formed on the surface of these alloys is meant to be the barrier between the metal and the corrosive environment. The deterioration of this protective layer limits the lifetime of these alloys. A better understanding of the transport phenomena, which take place in the oxide layer during oxidation, could be beneficial for the development of more resistant alloys.</p><p>In the present study, oxygen and hydrogen transport through the zirconia layer during oxidation of Zr-based materials at temperatures around 400C have been investigated using the isotope-monitoring techniques Gas Phase Analysis and Secondary Ion Mass Spectrometry. The processes, which take place at oxide/gas and oxide/metal interface, in the bulk oxide and metal, have to be considered in the investigation of the mechanism of hydration and oxidation. Inward transport of oxygen and hydrogen species can be influenced by modification of the surface properties. We found that CO molecules adsorbed on Zr surface can block the surface reaction centers for H₂ dissociation, and as a result, hydrogen uptake in Zr is reduced. On the other hand, coating the Zr surface with Pt, resulted in increased oxygen dissociation rate at the oxide/gas interface. This generated enhanced oxygen transport towards the oxide/metal interface and formation of thicker oxides. Our results show that at temperatures relevant for the nuclear industry, oxygen dissociation efficiency decreases in the order: Pt > Zr₂Fe > Zr₂Ni > ZrCr₂ ≥ Zircaloy-2.</p><p>Porosity development in the oxide scales generates easy diffusion pathways for molecules across the oxide layer during oxidation. A novel method for evaluation of the gas diffusion, gas concentration and effective pore size of oxide scales is presented in this study. Effective pore sizes in the nanometer range were found for pretransition oxides on Zircaloy-2.</p><p>A mechanism for densification of oxide scales by obtaining a better balance between inward oxygen and outward metal transport is suggested. Outward Zr transport can be influenced by the presence of hydrogen in the oxide/metal substrate. Inward oxygen transport can be promoted by oxygen dissociating elements such as Fe-containing second phase particles. The results suggest furthermore that a proper choice of the second-phase particle composition and size distribution can lead to the formation of dense oxides, which are characterized by low oxygen and hydrogen uptake rates during oxidation.</p>

The trend for designing of a titanium implant explored using different chemical compositions and crystallinity materials until people realized that the implant surface character was another important factor affecting the rate and extent of osseointegartion. Titanium received a macroporous titania surface layer by anodization, which contains open pores with average pore diameter around 5μm. An additional mesoporous titania top layer was created that followed the contour of the macropores and having 100–200 nm thickness and a pore diameter of 10 nm. Thus, a coherent laminar titania surface layer was obtained producing a hierarchical macro- and mesoporous surface. The interfacial bonding between the surface layers and the titanium matrix was characterized by a scratch test that confirmed a stable and strong bonding of the laminar titania surface layers upon titanium. The wettability to water and the effects on the osteosarcoma cell line (SaOS-2) proliferation and mineralization of the formed titania surface layers were studied systematically by cell culture and scanning electron microscopy (SEM). A synergistic role of the hierarchical macro- and mesoporosities was revealed in terms of enhancing cell adhesion, proliferation and mineralization, when compared with the titania surface with solo porosity scale topography. For the in vivo results of the evaluation of osseointegration, an argon ion beam polishing technique was applied to prepare the cross sections of implants feasible for the high resolution SEM investigation. The interfacial microstructure between newly formed bone and implants with four modified surfaces including the new hierarchical macro- and mesoporous implant surface retrieved after in vivo tests were characterized. By this approach it has become possible to directly observe early bone formation, the increase of bone density, and the evolution of bone structure. The two bone growth mechanisms, distant osteogenesis and contact osteogenesis, can also be distinguished. These direct observations give, at microscopic level, a better view of osseointegration and explain the functional mechanisms of various implant surfaces for osseointegration. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: In press. Paper 4: Manuscript.</p>

Network structures based upon metal-organic backbones represent a new class of functional materials that can be rationally constructed by employing the concepts of supramolecular chemistry and crystal engineering. The modularity of design strategies, the diversity of prototypal structures, and the dynamic features of networks have afforded great advantages over traditional materials syntheses. The research presented in this dissertation is primarily concerned with developing an in-depth understanding of the basic principles that govern the supramolecular behaviors of metal-organic frameworks and gaining an experimental control over the structure and function of these new classes of hybrid materials. The use of rigid and angular organic ligands along with transition metal clusters gives rise to a wide variety of novel metal-organic architectures ranging from zero-dimensional nanostructures to three-dimensional frameworks. Gas sorption experiments suggest some of these compounds are potentially useful as porous materials. Conformational analysis of these structural models reveals geometrical foundations for the existence of superstructural diversity. Controlled crystallization experiments further indicate synthetic factors that might determine the formation of supramolecular isomers. On the other hand, careful selection of more labile organic components leads to flexible metal-organic frameworks exhibiting dynamic characteristics that have not been observed in their rigid counterparts. The guest-dependent switch-on/off of cavities and the ease of fine-tuning their chemical environments demonstrate the effectiveness of such a strategy in the context of generating tailored functional materials. Discovery and recognition of novel three-periodic metal-organic nets remains a nontrivial exercise. In this context, rigorous topological analysis assists the understanding of complicated nets and application of geometrical principles facilitates desing of new metal-organic structures. Finally, scaled-up metal-organic frameworks are potentially accessible with the aid of existing prototypal structures and a systematic study on ligand design.

<p><font face="TimesNewRoman"> <p align="left">Research findings in current study provide a new insight into the fractured rock aquifers in the TMG area. Some of the results will have wide implications on the groundwater management and forms a solid basis the further study of the TMG aquifers.</p> </font></p>

The focus of this dissertation is on the development of a solid freeform fabrication (SFF) process for the design and manufacture of porous biodegradable orthopaedic implants from calcium polyphosphate (CPP). Porous CPP structures are used as bone substitutes for regenerating bone defects and/or as substrates in formation of so-called “biphasic” implants for repair of damaged osteochondral tissues. The CPP implants can be utilized in the treatment of many musculoskeletal diseases, osteochondral defects, and bone tumours while replacement of the defect site is required. In this study, the fabrication of CPP structures was developed through a powder-based SFF technique known as adhesive bonding 3D-printing. SFF is an advanced alternative to the “conventional” fabrication method consisting of gravity sintering of CPP pre-forms followed by machining to final form, as SFF enables rapid manufacturing of complex-shaped bio-structures with controlled internal architecture. To address the physical and structural properties of the porous SFF-made components, they were characterized using scanning electron microscopy, micro-CT scanning and mercury intrusion porosimetry. Specific surface area and permeability of the porous structures were also determined. Additionally, the chemical properties (crystallinity) of the specimens were identified by X-ray diffraction. The mechanical properties of the crystalline CPP material were also measured by micro- and nano-indentation. Moreover, the porous structures were tested by uniaxial and diametral mechanical compression to determine the compressive and tensile strengths, respectively. Furthermore, the effect of the stacked-layer orientation on the mechanical properties of the SFF-made constructs was investigated through the production of samples with horizontal or vertical stacked-layers. The properties of the SFF-made samples were compared with those of the conventionally-made CPP constructs. The SFF-made implants showed drastically higher compressive mechanical strength compared to the conventionally-formed samples with identical porosity. It was also shown that the orientation of the stacked-layer has substantial influence on the mechanical strengths. Moreover, this thesis examined the ability of in vitro forming of cartilaginous tissue on the SFF-made substrates where the chondrocytes cellular response to the CPP implants was evaluated histologically and biochemically. In addition, an initial in vivo assessment of the CPP structures as bone substitutes was conducted using a rabbit medial femoral site model. Significant amount of new-bone was formed within the CPP porous constructs during the 6-week implantation period demonstrating appropriate biological response of SFF-made CPP structures for bone substitute applications. Another accomplishment of this thesis was the development of a mathematical model which predicts the compact density of powder layers spread by a counter-rotating roller in the SFF technique. The results may be used in the control of the apparent density of the final implant. The potential of the developed SFF method as an efficient and reproducible technique for the production of porous CPP structures for use in orthopaedics and musculoskeletal tissue regenerative applications was concluded.

Laplace transform step-response functions are presented for one dimensional transient flow in fractured semi-infinite &amp / finite aquifers. Unsteady flow in the aquifer resulting from a constant discharge pumped from the stream is considered. Flow is one-dimensional, perpendicular to the stream in the confined aquifers. The stream is assumed to penetrate the full thickness of the aquifer. The aquifers may be semi-infinite or finite in width. The Laplace domain solutions are numerically inverted to the real-time domain with the Stehfest (1970) algorithm. During the course of the thesis a simple computer code is written to handle the algorithm and the code is verified by applying it to the one-dimensional transient flow in a semi-infinite homogeneous aquifer problem which can be solved analytically to crosscheck with the numerical results.

[Truncated abstract] This thesis describes the development of synthetic rock samples, representative of core samples from hydrocarbon reservoirs. The basic process consists of screening and sorting silica particles into discrete grain sizes, and then binding them together using a proprietary process known as CIPS, (Calcite In-situ Precipitation System). In the bonding process, the porosity of the system is substantially preserved, and the technique allows the manufacture of synthetic core samples with a tailor-made permeability. The produced samples were extensively characterised using a variety of analytic techniques to determine their porosity, permeability and pore size distribution. These analyses were a necessary pre-cursor to a major part of this thesis: the characterisation of the pore space by nuclear magnetic resonance (NMR) techniques. The synthetic core samples, covering a 7 times factor in grain sizes were examined using NMR, and this data formed the comparative basis for the NMR studies that followed. Two fundamental NMR questions were posed and answered in this thesis: 1. What is the effect of paramagnetic ions in the rock matrix on the NMR response? In pursuit of this question the CIPS process was extended to include co-precipitation of paramagnetic ions. A key feature is that the ions were deposited in predictable amounts at known sites (on the wall of the pore space). ... The NMR response in these double cores was then measured and examined to provide an answer to the question posed at the beginning of this paragraph. The significance of this work is that the physically distinct cores are a cylindrical analogue of adjoining sedimentary strata. By answering the question posed above, the thesis gives an indication of the vertical porosity resolution ultimately possible in an NMR logging tool. At present this ranges from 9” to 24” in the most favourable circumstances. This work suggests that the NMR signal carries porosity information at a much higher resolution, and that advanced numerical analysis of the NMR signature could realise the potential of greater stratigraphic resolution in NMR logging In addition to the research outlined above, the application of the CIPS technique to produce analogues of reservoir rocks, pioneered in this thesis, has stimulated similar research to be undertaken at other institutions, including the fabrication of synthetic reservoir cores containing clay particles (at CSIRO - the Commonwealth Scientific and Industrial Research Organisation) and a large scale application, formation of meter size blocks of CIPS bonded material, with separate strata, for laboratory studies of seismic waves (at Curtin University)