Sustainable chemically modified poly(butylene adipate- co -terephthalate)/thermoplastic starch/poly( ε -caprolactone)/cellulose biocomposites: looking at the bulk through the surface

Sustainable polymer composites (or biocomposites) based on renewable and green polymers are progressively under development in a technological paradigm shift from “just use more and more” to “convert into value-added products”. Therefore, significant efforts should focus not only on their reduced environmental impact but also on maximizing their performance and broadening their application range. Herein, the bio-based blends based on Mater-Bi bio-plastic and poly( ε -caprolactone), at a weight ratio of 70:30, were developed, followed by the addition of UFC100 cellulose filler to yield sustainable biocomposites. The effects of cellulose chemical modification with three diisocyanates, i.e., hexamethylene diisocyanate (HDI), methylene diphenyl isocyanate (MDI), or toluene diisocyanate (TDI) on the surface properties of biocomposites were evaluated by water contact angle and surface roughness detected by atomic force microscopy (AFM). Biocomposites containing cellulose modified with HDI, MDI, or TDI revealed contact angle values of 93.5°, 97.7°, and 92.4°, respectively, compared to 88.5° for reference blend, indicating an enlarged hydrophobicity window. This action was further confirmed by increased fracture surface roughness and miscibility detected by microscopic observation (scanning electron microscopy (SEM) and AFM). An in-depth oscillatory rheological evaluation has identified MDI, followed by TDI, as the most efficient compatibilizer of the analyzed system. Correspondingly, thermogravimetric analysis and differential scanning calorimetry analyses showed more residue and higher melting temperatures for biocomposites, more promisingly with MDI and TDI modifiers. In conclusion, either incorporation or diisocyanate modification of cellulose affects both surface and bulk properties, providing vital insights into future developments in the field. Proper selection of diisocyanate modifier of cellulose may enable engineering of composites performance.