The Effects of TiO2 and MontmorilloniteNanofillers on Structural, Thermal and Optical Properties of Starch based Nanobiocomposite Films

Biodegradable films for food packaging applications have attracted an increasing amount of consideration over the last two decades, predominantly due to environmental pollution and the realization that our petroleum resources are not infinite. Starch, which is one of the natural biopolymers, has been considered as one of the best candidates primarily because of its processbility, availability and price. The main disadvantages of starch films are their pronounced hydrophilic character therefore; they are permeable to water vapor and have usually poor mechanical properties. However, these features can be significantly improved by blending with nanodimension materials such as Montmorillonite (MMT) and Titanium dioxide (TiO2). The main reason for this improvement in comparison with conventional composites is the large surface area which results in high interactions between the nanofillers and polymer when these nano-materials are well dispersed. The behavior of nanocomposite films has been depended to the dispersion of the nanoparticles in the polymer matrix. MMT as a one-dimensional (1D) material is the most commonly used layered silicates. TiO2 as three-dimensional (3D) nanoparticle has been investigated most widely because it is inert, inexpensive and, has a high refractive index with UV shielding potential. The study on films with different dimensions of nanofillers simultaneously is rarely reported. MMT and TiO2 as two inorganic nanofillers have different shapes and structures, so the combination of TiO2 and MMT apparently had a synergistic effect on the starch film properties. The aim of this study was to control particle agglomeration and investigate the synergistic effect of combination of TiO2 nanoparticles and MMT layers and on the surface topography, color, and thermal properties of plasticized starch-MMT-TiO2 nanocomposites.
.First, 100 ml of potato starch solution with a concentration of 4% (w/v) was prepared by dispersion of the starch in distilled water and was gelatinized at 80ºC for 15 min. Different levels of MMT (3 and 5% w/w starch) and TiO2 (0.5, 1 and 2% w/w starch) were dissolved in distilled water and were added to the gelatinized starch after treatment with ultrasound for 30 min. Glycerol, as a plasticizer, with concentrations of 50% (w/w starch) were added to the filmogenic solution. The plasticized starch (PS) based filmogenic solutions were dried in an oven at 45 °C for 15 hours. The surface roughness and topography and thermal properties of the films were determined through atomic force microscopy (AFM) and differential scanning calorimetry (DSC) analysis, respectively. Fourier transforms infrared (FTIR) spectroscopy in the range of 4000 to 400 cm-1. UV-Vis spectroscopy was employed to evaluate the absorbance and opacity behavior of the PS-MMT-TiO2 nanocomposite films in the wavelength range of 200-800 nm. The color parameters of films were measured by a portable colorimeter. Statistical analysis was performed on a completely randomized design with the analysis of variance (ANOVA) and Duncan’s multiple range tests was used to detect differences among the mean values of the films properties
Atomic force microscopy’s images demonstrated an obviously uniform dispersion of MMT and TiO2 nanomaterials in the PS-3%MMT-TiO2matrix with smoother surfaces and a lower roughness parameters than that for the corresponding binary PS-MMT nanocomposites with the MMT filler content (3 wt%). Surface roughness of starch films was changed depending on the MMT and TiO2 content. The results of the roughness parameters and topographic images were confirmed by the high frequency distribution curves. In the PS-3 and 5% MMT films, most parts have height of about 400 and 600 nm, respectively; While the height of the PS-MMT-1% TiO2 bionanocomposites film were 200 and 800 nm. FTIR revealed the hydrogen bonds and electrostatic interactions between nanofillers with starch and themselves by the peaks associated with bond C-O-H at 1142 cm-1 and 990 cm-1 and wide and high intensity IR absorption in the 500-800 cm-1.Evanescence of 3626 and 3452 cm-1 peaks assigned to OH groups of MMT in the PS-3MMT spectrum affirmed the interaction between starch and MMT.Shift in melting temperature and glass transition (Tg) towards higher temperature respectively from 295.1C to 306.3 C and from 199.1 C to 207.6 C were illustrated by DSCresults due to addition of TiO2 in the PS-3%MMT matrix.Improvement of thermal stability might be attributed much jammed and conjugated 3D MMT-TiO2 network combined together, or powerful interaction between PS and nanofillers could also slowdown the polymer chains motion and melting point during heating. These results showed a significant effect of combination of 1D MMT layers and 3D TiO2 nanoparticles on the thermal properties of PS nanobiocomposite starch based films. Montmorillonite did not affect color of nanocomposite. The transparency of a nanobiocomposite film is not significantly varied when the clay layers with about one nm thick are excellent dispersed through the polymer matrix, since such MMT platelets are less than the of visible light wavelength and do not block lights transmission. Transmittance, redness and yellowness of new ternary films decreased when TiO2 was added to PS-3%MMT matrix at 1%. In this case, color difference (ΔE) and whiteness index (WI) are increased 86.6% and 76% respectively.Starch and PS-MMT films were colorless. The presence of TiO2 imparted whiteness to the nanocomposites due to its inherent whiteness. This phenomenon can be enucleated as the large specific surface area and high refractive index of nanosized TiO2 particles were accounted or diffuse reflection of light from the interface of the materials, and consequently, transparency loss of the composite films. UV-Vis spectroscopy was employed to evaluate the absorbance and opacity behavior of the PS-MMT-TiO2 nanocomposite films in the wavelength range of 200-800 nm. Incorporation of TiO2 nanoparticles into the starch film solution caused a significant decrease of transmittance in visible, UV-A (360 nm), UV-B (300 nm), and UVC (240 nm) regions. The results of UV-Vis spectroscopy showed that this type of films could be used as a packaging material to shield against UV and visible light.