Seyed Amir Oleyaei; Babak Ghanbarzadeh; Ali Akbar Moayedi; Parisa Poursani; Fateme Mousavi Baygi; Mohammad Reza Bakhsh Amin
Abstract
Introduction: Biopolymers are a class of polymer, which are disintegrated by an enzymatic or bio-path and the products disseminated to the surroundings do not induce negative effects. Nowadays, non-degradable polymers are quid pro quo with biodegradable ones particularly in agricultural applications, ...
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Introduction: Biopolymers are a class of polymer, which are disintegrated by an enzymatic or bio-path and the products disseminated to the surroundings do not induce negative effects. Nowadays, non-degradable polymers are quid pro quo with biodegradable ones particularly in agricultural applications, environmental and food industry use. Starch is an example of natural biopolymers, biocompatible, which is completely biodegradable in environment. It has been considered as one of the best candidates for oil based polymer substitution due to its low cost, availability and processbility. The main disadvantages of starch based polymers are their high hydrophilic nature therefore; they have poor mechanical properties and are permeable to water vapor. However, these aspects could be considerably reclaimed by shuffling it with nanodimension materials such as itanium dioxide (TiO2) and Montmorillonite (MMT). The main reason for this improvement in comparison with conventional composites is the large surface area of these nanomaterials which results in high interactions between the nanofillers and starch. The functional behaviors of nanocomposite films have been depended to the compatibility and degree of nanoparticles dispersion in the biopolymer matrix. TiO2 is a 3D nanosphere has been perused widely because it is inexpensive, chemical inert and, has a high refractive index with visible and UV shielding potential. MMT as a 1D, platelet is the most commonly used layered silicates. The investigation of biodegradable films containing two different nanofillers simultaneously has been rarely done. TiO2 and MMT as two different inorganic nanofillers have different physical and chemical structures, so simultaneously use of TiO2 and MMT clearly had a new effect on the nanoparticle distribution and functional properties of starch films. The aim of this study was investigate the synergistic or antagonistic effect of combination of TiO2 nanoparticles and MMT platelets on the functional properties such as surface hydrophobicity, water vapor permeability (WVP), moisture uptake (MU), Water Solubility (WS) and mechanical properties of plasticized starch-MMT-TiO2 nanocomposites.
Materials and methods: 100 ml of potato starch solution with a concentration of 4% (w/v) was prepared by dispersion of starch in distilled water. It was gelatinized at 80 ºC for 15 min. Different amount of TiO2 (0.5, 1 and 2% w/w starch) and MMT (3 and 5% w/w starch) were dissolved in distilled water and added to the gelatinized starch after treatment with ultrasound for 30 min. Glycerol with concentration of 50% (w/w starch) was added to the starch-nanofillers filmogenic solution. Bionanocomposite plasticized starch (PS) films were produced by casting and were dried in an oven at 45 °C for 15 hours. The X-Ray diffraction (XRD) measurements were performed for MMT and TiO2 powder and starch-MMT and –TiO2 nanocomposite films. The methodology of WVP measurements was based on the ASTM E96-05 (ASTM, 2005). Mechanical properties of the films were determined according to ASTM standard method D882-10 (ASTM, 2010). With some modifications, the methods described by Tunc et al., (2007) and Rhim et al., (2006) were used to determine MU and WS, respectively. Water contact angle (WCA) measurements were performed by the sessile drop procedure. The statistical analyses on a completely randomized design and were carried out using analysis of variance (ANOVA). Duncan’s multiple range test (p < 0.05) was used to detect differences among the mean values of the functional properties.
Results and discussion: XRD demonstrated the change of MMT layers dispersion pattern from exfoliation in binary PS-5%MMT films to exfoliation-intercalation in ternary PS-5MMT-TiO2 films. These results showed that TiO2 agglomerates are formed in the starch matrix with MMT level more than 3% wt. This could be due to the interaction between starch and MMT tends to be more favorable than TiO2. Good dispersion of TiO2, high miscibility of with clay, and continuous phase can be obtained when the content of MMT discs is low. Due to the strong interfacial interaction between the starch and MMT, the tensile strength (TS) increased considerably from4.86 to 5.24 MPa, while the elongation at break (EB) decreased significantly from 78.23 to 71.93%, As the MMT concentration varied from 3 to 5%. The TS of nanocomposite films were further improved after the incorporation of TiO2. Suitable dispersal of TiO2, and creation of new interactions in the PS-MMT network, causes to increase the tensile strength of nanocomposites. The TS and EB values of PS-3MMT-1TiO2 nanocomposite film was higher than that of the other films. This is indicative of a synergistic effect between TiO2 and MMT which increases the tensile strength and does not decrease the EB. In the PS-5% MMT films, both mechanical characteristics were reduced. WVP shows more evidences of synergistic effect of combination of 1D MMT and 3D TiO2 on starch films. WVP reduction by MMT has been attributed to tortuous pathway which created by clay layers in the starch matrix. MMT platelets are water vapor impermeable, thus exfoliation of MMT reduce the voids in starch matrix. The PS-3MMT-2TiO2 nanocomposite showed the lowest WVP as compared to other PS films. WVP was reduced significantly from 5.84 × 10-7 g/m.h.Pa in the PS-3%MMT binary film to 3.04 × 10-7 g/m.h.Pa in the PS-3%MMT-2%TiO2 ternary film. TiO2 have low water solubility and hydrophobicity compared with starch and MMT. Thus, significant decrement of WVP in the prophase of TiO2 connoted that TiO2 was obstructing the nano- and micro-pathways in the PS films network. With addition of MMT and TiO2 content the water solubility and moisture absorption were reduced significantly. Results of water contact angle test confirmed the results of moisture absorption, solubility in water and water vapor permeability and showed that the addition of TiO2 increased the surface hydrophobicity of starch-MMT films as with addition of 2% titanium dioxide in PS-3% MMT and PS-5% MMT films, the contact angle after 60 seconds increased 4 and 15 degree respectively. As a result, 1% wt TiO2 nanoparticles (FDA maximum allowable) can be regarded as the optimum concentration and the developed starch based nanocomposite films can enable undertaking applications as appropriate candidates in food packaging systems.
Seyed Amir Oleyaei; Babak Ghanbarzadeh; Ali Akbar Moayedi; Farhang Abbasi
Abstract
Introduction: 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, ...
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Introduction: 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.Materials and methods:.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 propertiesResults and discussion: 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.
