Cassava starch was blended with glycerol using a co-rotating twin-screw extruder (TSE). Thermoplastic cassava starch (TPCS) at a ratio of 70/30 by weight of cassava/glycerol was selected and further blended with other polymers. TPCS sheets made from compression molding had low tensile strength (0.45 ± 0.05 MPa) and Young's modulus (1.24 ± 0.58 MPa), but moderate elongation at break (83.0 ± 0.18.6%), medium level of oxygen permeability, and high water vapor permeability with a very high rate of water absorption. TPCS was blended with poly(lactic acid) (PLA) at various ratios by using a TSE. The blend resins exhibited good properties such as increased thermal stability (Tmax) and crystallinity of PLA, and improved water sensitivity and processability of TPCS. PLA and TPCS exhibited a high interfacial tension between the two phases of 7.9 mJ*m-2, indicating the formation of an incompatible, immiscible blend. SEM micrographs showed a non-homogeneous distribution of TPCS droplets in the PLA continuous phase. TEM micrographs of the blend films made by cast-film extrusion showed coalescence of the TPCS droplets in the PLA continuous phase of the blend, indicating that the compatibility between the polymer pair needs to be improved. A response surface methodology (RSM) design was used to analyze the effects of maleic anhydride (MA) and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (Luperox or L101) contents, and TSE screw speed on the degree of grafted MA and number average molecular weight (Mn) of functionalized PLA (PLA-g-MA), a reactive compatibilizer. PLA-g-MA made by reactive extrusion had an array of colors depending on the content of L101 and MA used. New FTIR peaks suggested that MA was grafted onto the PLA backbone and oligomeric MA may occur. Increasing L101 increased the degree of grafting and decreased Mn, but the Mn of the PLA-g-MA's produced with a high amount of L101 was stable during storage. MA exhibited an optimum concentration for maximizing the degree of grafted MA, and increasing MA content retarded the reduction of Mn during processing. However, the Mn of PLA-g-MA during storage decreased more rapidly with a high content of MA. TSE screw speed had an impact on the Mn with the maximum value predicted at 20 rpm. PLA-g-MA compounds differing in Mn and/or grafted MA content were used as reactive polymers with TPCS (to produce binary blends) and as reactive compatibilizers (to produce ternary blends of PLA/TPCS/PLA-g-MA) with TPCS content of 30 wt% using a TSE. As a result of maleation, PLA-g-MA had a higher grafted MA content with a lower Mn, and higher PI. The interaction of anhydride groups from PLA-g-MA and hydroxyl groups from TPCS was found by FTIR. The reactive binary blends exhibited a change in thermal stability, decrease of Tcc, the presence of double melting peaks, and an increase of the Tgs of glycerol and starch. The higher the grafted MA content and/or the higher Mn of the PLA-g-MA used, the better were the distribution and smaller the TPCS domains obtained in the blends. The highest elongation at break was achieved when 30 wt% TPCS was blended with 70 wt% of PLA having 0.1 wt% of grafted MA and Mn of PLA-g-MA with a 45 kDa. Finally, the optimum PLA-g-MA was determined by using the results from PLA-g-MA RSM design and the reactive blending.
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