Synthesis of HAP nano rods and processing of nano-size ceramic reinforced poly(L)lactic acid composites

Bone is unique among the various connective tissues in that it is a composite of organic and inorganic components. Calcium phosphates occur principally in the form of hydroxyapatite crystals {lcub}Ca₁₀(PO₄) ₆(OH)₂{rcub}. Secreted apatite crystals are integral to the structural rigidity of the bone. When a bone breaks, there is often a need to implant an orthotic device to support the broken bone during remodeling. Current technologies use either metal pins and screws that need to be removed (by surgery) once the healing is complete or polymeric materials that either get resorbed or are porous enough to allow bone ingrowth. Poly(L)Lactic acid and copolymers of polyglycolic acid (PGA) are thermoplastics which show promise as the matrix material in biosorbable/load bearing implants. In service this material is hydrolyzed generating water and L-lactate. Orthoses composed of neat PLLA resins require greater than three years for complete resorbtion, however; 95% of strength is lost in 2 to 3 weeks in-vitro. This has limited the deployment of load bearing PLLA to screws, pins or short bracing spans. There exists a need for the development of an implantable and biosorbable orthotic device which will retain its structural integrity long enough for remodeling and healing process to generate new bone material, about 10 weeks.; The scope of this dissertation is the development of HAP nano-whisker reinforcement and a HAP/PLLA thermoplastic composite. As proof of the feasibility of generating nano-reinforcement PLLA-composites, the surface of a galleried clay, montmorillonite, was modified and clay/PLLA composites processed and then characterized. Hydroxyapatite nano-whiskers were synthesized and functionalized using organosilanes and Menhaden fish-oil (common organic dispersant). The functionalized nano-fibers were used to process HAP/PLLA composites. Characterization techniques included thermal analysis, magnetic spectroscopy, XRD and ICP analysis and electron microscopy.; The montmorillonite galleries were successfully intercalated and exfoliated. Gallery spacings increased as much as 30Å with ODA. NMR results demonstrated that the ODA in the galleries of the highly loaded clay is in an extended trans-configuration at lower temperatures. Furthermore the alkyl chains are nano-constrained and have limited mobility. These configurations influence the gallery spacing. The appearance of two crystalline melts (DSC) may indicate that the desired physicochemical modification of the PLLA at the clay nano-reinforcement interface was achieved. For the growth of HAP nano-rods a hydrothermal synthesis route was developed. A kinetics study revealed several unique features of the method of growth. TEM analysis indicates that the synthesis procedure was successful in generating rod-like HAP structures of 100nm length and 10 nm in width. The effect of synthesis conditions on the phase purity and the morphology of the precipitates was investigated. The surface of the HAP rods was modified using OTS and OMS. The surface modified HAP was used to process HAP/PLLA composites. The properties of the composites depend strongly on the nature of the interface. Composites made with OMS or OTS demonstrated a higher elastic modulus. At 1% solids loading the OTS treated sample generated a 40% increase in modulus. Silane treated composites had DMA transitions shifted 10 to 20 degrees higher. “Well-ordered” SAMs improve the dispersion of the inorganic reinforcement in PLLA and promote the formation of mechanical entanglements at the HAP-PLLA interface. As a result load transfer is more complete resulting in higher modulus material.