Oxidative Degradation of Thermoplastic Starch Induced by UV Radiation

Among biopolymers,thermoplastic starch(TPS)is a good candidate to obtain biomaterials because of its natural origin,biodegradable character,and processability.Exposure to ultraviolet(UV)radiation causes significant degradation of starch-based materials,inducing photooxidative reactions which result in breaking of polymer chains,production of free radical,and reduction of molar mass.These changes produce a deterioration of TPS mechanical properties,leading to useless materials after an unpredictable time.In this work,changes induced on TPS by UV radiation,analyzing structural properties and mechanical behavior,are studied.TPS was obtained through thermo-mechanical processing of native corn starch in the presence of water(45%w/w)and glycerol(30%w/w)as plasticizers.Films were obtained by thermocompression and,before testing,specimens were conditioned to reduce material fragility.Photodegradation process was performed by exposing TPS to 264 h UV radiation in a weathering test chamber.Specimen’s weight loss was determined gravimetrically.Chemical changes were studied by Fourier Transform Infrared Spectroscopy(FTIR)and morphological modifications were analyzed by Scanning Electron Microscopy(SEM).Reduction of weight average molar mass was measured by Static Light Scattering(SLS).Changes in mechanical properties were studied from tensile tests.After 96 h exposure,TPS specimens presented a weight reduction of 4-6%,mainly attributed to plasticizers lost by evaporation.SEM observations showed that UV radiation induced morphological changes on TPS,evidenced by an increment of specimens cracking.By FTIR,it was detected the presence of an additional band located at 1726 cm-1 in samples submitted to UV radiation,attributed to the formation of-C=O groups.Weight average molar mass of native starch was in the order of 107 g mol-1.TPS exposure to UV radiation decreased significantly its molar mass,confirming molecular degradation of the biopolymer.When TPS was exposed during 48 h,it was detected a considerable decrease in elongation at break values(~85%),indicating that TPS flexibility was reduced.On the other hand,after 48 h exposure,TPS elastic modulus was 55 times higher than those of the unexposed specimens,evidencing an increase in material rigidity.TPS maximum tensile strength was also increased by UV light,with an increment of^400%after 48 h exposure.Results revealed that starch-based materials can be degraded by exposure to UV radiation,modifying their microstructure and mechanical performance.

Biocomposites Based on Thermoplastic Starch and Granite Sand Quarry Waste

Granite stone is a by-product of the rock crushing manufacturing.An industrial waste in powder form that causes health problems and environmental pollution.Fine particles fraction can be used as a partial replacement of sand in concrete manufacture.In this work,an alternative exploitation of this waste fraction is proposed.Granite sand(GS)with particles mean size of ~1μm was employed as thermoplastic starch(TPS)filler at different concentrations.Biocomposites were obtained by melt-mixing and thermo-compression,achieving translucent and easy to handle films.A good GS dispersion within the matrix was evidenced by SEM.Mineral presence induced a shift of starch’s melting point to higher values and a better thermal resistance.TPS UV absorption capacity was increased ~90% by GS addition.An increment in TPS Young’s modulus and maximum tensile stress of 5 and 3 times,respectively was observed by adding 5%w/w GS.