Crystallization kinetics and affecting parameters on polycaprolactone composites with inorganic and organic additives

Abstract

The isothermal crystallization and mechanical behavior of biodegradable polycaprolactone (PCL) composites with organic (oleic acid and glycerol monooleate) and inorganic (zinc oxide, organoclay, and hydroxy apatite) additives used alone or simultaneously were investigated. The effect of all additives on the degree of crystallinity percentage (DOC%), isothermal crystallization kinetics parameters, and mechanical test results of PCL composites was studied. The PCL composite films were prepared by solvent casting by using dichloromethane as the solvent. The films were characterized by X-ray diffraction, differential scanning calorimetry (DSC), and tensile tests. DSC of the first melting and X-ray diffraction DOC% results (for composites by solvent casting) are compatible. The values by DSC of the second melting (for composites by extrusion method) are lower. Organoclay gives the highest crystallinity among the other inorganic additives used. Small amounts of inorganic additives act as a nucleating agent and increase the crystallinity; the higher amounts decrease. The organic additives act as the plasticizer. When used alone, it lowers the crystallinity, but when used with inorganic additives, it improves the dispersion of inorganic particles in the polymer matrix. The isothermal crystallization kinetics parameters by Avrami analysis showed that crystallization was controlled by nucleation and the crystals had spherical structure. The nucleation type changed between thermal and athermal nucleation. The Pukanzky model interaction parameter B indicated that the organic additives improved the dispersion of inorganic particles in the polymer matrix. Statistically significant, eight correlations (F>6) were obtained for the crystallinity, crystallization parameters, Young's modulus, and tensile strength as a function of concentration of additives.