Synthesis of Hydroxyapatite/Nanocellulose Composites

Cellulose nanocrystals (CNC) are great candidates for composite materials. The reasons why CNCs are such attractive materials for them are due to their great mechanical properties, high aspect ratio and low density. On the other hand, hydroxyapatite (HAp) is a kind of calcium phosphate and a main component of bones and teeth. The purpose of the present study is to make oriented nano-sized composites with CNC and HAp. Although some researchers carried out to make CNC composites with HAp for biomedical materials, nano-sized and oriented ones haven’t been achieved yet. Also, films made of CNC and other compounds are known to be transparent and have good oxygen permeability. Especially when CNCs’ direction is in parallel, they show high strength. However most previous researches dealt with particles or plate-like minerals in inorganic/CNC films, so there is no case that coated CNCs themselves were aligned in the films. Therefore fabrication of composite-oriented thin films is quite unique and it will be a potential step for bone-like hierarchical structure. In experiment, certain amount of CNC suspension with functional groups were put into revised simulated body fluid (r-SBF) solutions which were adjusted between pH 6.9-7.9 to make the molar ratio of calcium ion per functional groups on CNC surfaces between 30-230. The suspensions were put into the ultrasonic bath for 15 minutes and stirred in the thermostatic oven at 37 ⁰C for 1 hour. The process of ultrasound and stirring in oven was repeated 1-3 times depending on conditions. Precipitated products were collected with the centrifuge instrument and dried with the freeze dryer. Functional groups induced HAp’s nucleation and the HAp/CNC composites could be obtained under control of molar ratio of calcium ions per functional groups on CNC and pH. Morphology of the composites could be determined by pH and HAp content could be controlled between 25-75 wt% by initial molar ratio. The suspension having the composites synthesized in pH 7.9 with low initial molar ratio was dropped on superhydrophilic glass substrates. At the moment, the substrates were set with leans of 20 degrees. Then they were dried at 60 oC for 3 hours and transparent films containing 25-40 wt% of HAp were obtained. The transmittances of the films were more than 90 % and their thicknesses were 2.2-4.2 μm. The films were suggested to have oriented structure by polarization microscope when the shape of the composites were needle-like homogeneously and independent each other. From the results from SEM, they were aligned longitudinally at both ends of the film and laterally at the upper middle part of the films. It is considered that controlling drying direction influenced on the orientation. The current study should become a promising step to build up a bone-like hierarchical structure artificially