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.

The focus of this dissertation is on the development of an additive manufacturing system and methodology for fabricating structures with functionally graded porous internal properties and complex three-dimensional external characteristics. For this purpose, a multi-scale three-dimensional printing system was developed, with capabilities and fabrication methodologies refined in the context of, but not limited to, manufacturing of porous bone substitutes. Porous bone implants are functionally graded structures, where internally, the design requires a gradient in porosity and mechanical properties matching the functional transition between cortical and cancellous bone regions. Geometrically, the three-dimensional shape of the design must adhere to the anatomical shape of the bone tissue being replaced. In this work, control over functionally graded porous properties was achieved by integrating specialized modules in a custom-made additive manufacturing system and studying their effect on fabricated constructs. Heterogeneous porous properties were controlled by: (i) using a micro-syringe deposition module capable of embedding sacrificial elements with a controlled feature size within the structure, (ii) controlling the amount of binder dispersed onto the powder substrate using a piezoelectric printhead, (iii) controlling the powder type or size in real-time, and/or (iv) selecting the print layer stacking orientation within the part. Characterization methods included differential scanning calorimetry (DSC)-thermo gravimetric analysis (TGA) to establish the thermal decomposition of sacrificial elements, X-ray diffraction (XRD) and dispersive X-ray spectroscopy (EDAX) to investigate the chemical composition and crystallinity, scanning electron microscopy (SEM) and optical microscopy to investigate the physical and structural properties, uniaxial mechanical loading to establish compressive strength characteristics, and porosity measurements to determine the bulk properties of the material. These studies showed that the developed system was successful in manufacturing embedded interconnected features in the range of 100-500 $ \mu m $, with a significant impact on structural properties resulting in bulk porosities in the range of 30-55% and compressive strength between 2-50 MPa. In this work, control over the the three-dimensional shape of the construct was established iteratively, by using a silhouette extraction image processing technique to determine the appropriate anisotropic compensation factors necessary to offset the effects of shrinkage in complex-shaped parts during thermal annealing. Overall shape deviations in the range of +/- 5-7 % were achieved in the second iteration for a femoral condyle implant in a sheep model. The newly developed multi-scale 3DP system and associated fabrication methodology was concluded to have great potential in manufacturing structures with functionally graded properties and complex shape characteristics.

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.

This thesis describe methods to improve the interfacial stability of an interpenetrating phase composite (IPC) polyvinylurethanecarbonate), and to increase the hydrophobicity of the polymer phase. The current IPCs introduce covalent bonding between the phases via silanizing agents to enhance the interfacial stability. Incorporation of the silanizing agents was also intended to reduce the IPC’s sensitivity to interfacial hydration, thereby enhancing the IPC’s resistance to degradation during aging. Lysine diisocyanate was used to increase the hydrophobic character in the polyvinylurethanecarbonate resin. The polymer resins were infiltrated into porous CPP blocks with 25 volume% interconnected porosity and polymerized to produce the IPCs. After mechanical testing following a aging study it was found that the silanizing agents contributed to stability of the mechanical properties under aqueous conditions. It was concluded that the mechanical properties and stability were comparable to available biodegradable composites, as well as being biocompatible to a preosteoblast model cell line.

This thesis describe methods to improve the interfacial stability of an interpenetrating phase composite (IPC) polyvinylurethanecarbonate), and to increase the hydrophobicity of the polymer phase. The current IPCs introduce covalent bonding between the phases via silanizing agents to enhance the interfacial stability. Incorporation of the silanizing agents was also intended to reduce the IPC’s sensitivity to interfacial hydration, thereby enhancing the IPC’s resistance to degradation during aging. Lysine diisocyanate was used to increase the hydrophobic character in the polyvinylurethanecarbonate resin. The polymer resins were infiltrated into porous CPP blocks with 25 volume% interconnected porosity and polymerized to produce the IPCs. After mechanical testing following a aging study it was found that the silanizing agents contributed to stability of the mechanical properties under aqueous conditions. It was concluded that the mechanical properties and stability were comparable to available biodegradable composites, as well as being biocompatible to a preosteoblast model cell line.