Seyed Mahdi Ojagh; Akbar Vejdan Taleshmikaeil; Mehdi Abdollahi
Abstract
Introduction: Natural polymers have gained increasing attention for the development of packaging to reduce ecologically-related problems caused by plastic packaging (environmental pollution). Among these natural polymers, proteins such as gelatin is considered a good candidate for food packaging. However, ...
Read More
Introduction: Natural polymers have gained increasing attention for the development of packaging to reduce ecologically-related problems caused by plastic packaging (environmental pollution). Among these natural polymers, proteins such as gelatin is considered a good candidate for food packaging. However, several studies have shown that gelatin films are brittle, and their hydrophilic nature connotes high water vapor permeability and water solubility. Different solutions have been suggested to overcome these weaknesses, including adding crosslinking agents and chemical modification, adding nanoparticles and developing bio-film blends and bilayers with polysaccharides. Agar is a polysaccharide extracted from marine red algae, which is biocompatible, has good mechanical properties and possesses good film-forming properties. Preventing food spoilage from light and oxygen-induced oxidation is one of the greatest concerns in the food industry. Despite having good mechanical and relatively good water vapor permeability properties, protein- or polysaccharide-based films don't have sufficient barrier properties against oxygen and UV light that can't properly prevent the oxidation of food products. Among nanoparticles, metal oxides like TiO2 (such as antiradiation and antimicrobial activities) and Montmorillonite (such as improved mechanical and barrier properties against moisture, WVP and gases) have evidenced good potential to improve functional properties of bio-films. Thus, the present study aimed to develop a new biodegradable bilayer agar/gelatin film incorporating nanoclay and TiO2 for food packaging, with maximum water sensitivity and maximum UV light and oxygen barrier properties.
Materials and Methods: Agar/gelatin bilayer films were prepared by a two-step casting technique. First, the agar layer was produced by solubilization of 1.5 g of agar powder (agar-agar analytical grade were obtained from Merck Co., Germany) in 100 mL of distilled water. Then, glycerol (obtained from Merck Co., Germany) was added as plasticizer. The agar film-forming solution was casted onto petri-dish. In the next step, the gelatin (obtained from cold water fish skin was purchased from Sigma-Aldrich, St. Louis, MO, USA) solutions were prepared by dissolving 4 g of the fish gelatin in 100 mL of distilled water. Glycerol was also added as plasticizer. The TiO2 dispersions (in ratios of 0 and 2% of the gelatin) and MMT (Na+–montmorillonite (in ratios of 0, 3, 5 and 10% of the gelatin)) were added to the gelatin solution and stirred and sonnicated. Finally, produced solutions were then casted. The agar/gelatin films, with or without TiO2 and MMT, were characterized using SEM analysis. Film transparency, water vapor permeability, water solubility, swelling, surface color and mechanical properties of the bilayer films were also examined.
Results and Discussion: In this study, bilayer films based on agar and gelatin incorporated with TiO2-MMT nanoparticles have been successfully developed. Results demonstrated that some properties of the bilayer films were greatly influenced by TiO2 and MMT nanoparticle content. So that, the addition of TiO2 decreased water vapor permeability of the bilayers more than 15%, upon increasing TiO2 content to 2%. However, swelling ratio and moisture content increased with the increase in the nano-TiO2 content, probably due to the hydrophilic nature of the TiO2 nanoparticles. Also, whiteness index (WI) increased by adding 2% of TiO2 nanoparticles. As shown in the surface photograph of the bilayer films, TiO2 generated more opaque and whiter films, which might be related to the white color of TiO2 nanoparticles in solution form. Also, the addition of MMT (0, 3, 5, and 10%) to bilayer-2% TiO2 significantly decreased water vapor permeability and transmission of UV light of the bilayer films. However, tensile strength (TS) decreased with further increase of the nanoparticle concentration. Increasing the concentration of nanoparticles' MMT to 5%, the tensile TS of the agar/gelatin films increased from 12.86 to 20.54 MPa; it might also be related to the interactions between sulphydryl and carboxylic groups from certain amino acids in the gelatin structure with MMT and TiO2 nanoparticles. However, the TS decreased again with further increase of the filler content up to 10% MMT. Also, the addition of MMT from 3%-10% concentration significantly reduced the elongation at break value (EB) of the bilayer films from 41.77 to 28.90% for the bilayer films (p
Nazila Dardmeh; Asghar Khosrowshahi; Hadi Almasi; Mohsen Zandi
Abstract
Introduction: Nanocomposites are prepared by introduction of dispersed nanoscale particles into the polymer matrix based on four methods: template synthesis (sol-gel preparation); intercalation of polymer; and in situ intercalative polymerization and last one is melt blending, the most favorable and ...
Read More
Introduction: Nanocomposites are prepared by introduction of dispersed nanoscale particles into the polymer matrix based on four methods: template synthesis (sol-gel preparation); intercalation of polymer; and in situ intercalative polymerization and last one is melt blending, the most favorable and practical method due to its simplest, economical and environmentally friendly technic. This method involves annealing, statically or under shear, a mixture of the polymer and organically modified clay at the softening point of the polymer based on usual compounding devices, such as, extruders or mixers (Papaspyridesb 2008). PET is a semicrystalline thermoplastic polyester which has been extensively used in all sizes as a packaging material in direct contact with food, beverages and as an alternative packaging to polyvinyl chloride for edible oils (Kirwan et al. 2011). As polymeric nanocomposites are mainly used as structural materials, the layered silicate clay are preferred. The crystal lattice of 2:1 layered silicates, consists of two-dimensional layers where a central octahedral sheet of alumina is fused to two external silica tetrahedral by the tip. Montmorillonite (MMT) belongs to type 2:1 layered smectite clay which in the basic structure, the trivalent Al-cation in the octahedral layer is partially substituted by the divalent Mg-cation (Pavlidoua and Papaspyridesb 2008). As evident, MMT is greatly hydrophilic in the interlayer and incompatible with organic polymer such as PET, thus to increase compatibility of clay with polymer, inorganic inter-layer cations (Na+, K+ or Ca2+) exchanged by the cationic surfactants (e.g., quaternary ammonium salt). Modified MMT or organoclay interacts better with polymer due to its increased gallery space (Utracki et al. 2007; Parvinzadeh et al.2010). Three different types polymer/clay nanocomposites can be obtained depending on the preparation method and the nature of the components used, including polymer matrix, layered silicate and organic cation. Tactoid nanocomposites formed when stacks of modified layered silicates are retained after introduction into the polymer. Subsequently, interaction between the nanolayers and polymer is not only unsuccessful but reduces mechanical properties of composite as well. Our main objective of this research was to study the effect of the nanoclay addition on mechanical, colorimetric and transparency properties of poly (ethylene terephthalate) (PET) nanocmposite films. Materials and methods: Bottle-grade poly (ethylene terephthalate) granules with intrinsic viscosity of (IV) = 0.82 dl g-1 were provided by the Iranian Tondgooyan Petrochemical company. The organically modified montmorillonite, Cloisite 15A, was supplied by Southern Clay Products Inc. Standard of TPA was supplied from Fluka Chemical, trademarked Sigma-Aldrich Corp., Switzerland. High-pressure liquid chromatography (HPLC) grade water, aceto-nitrile, acetic acid and methanol (HPLC grade) were purchased from Merck (Darmstadt, Germany). TPA was dissolved into methanol with a slight increase in temperature. Working standard solutions were prepared on the day of use at concentrations of 0.4, 40, 100 and 1,000 ppb and calibration graphs were plotted using these concentrations of standard solutions. The PET granules and nanoclay particles were dried in an oven for 24 h at 110 and 80C before extrusion, respectively. Melt blending technique was used for preparing nanocomposite films in a co-rotating twin screw extruder ZSK 25 .The temperature profile (throat to die) was as follows: 250, 270, 275, 270, 270 and 265C with a screw speed of 250 rpm. PET granules were dry mixed with 1, 3, and 5% wt of Cloisite 15A. The total weight of material per batch was 300 g. The resulting nano-composite strand was cooled in a water bath, granulated and dried overnight in oven at 110C. A laboratory press with a temperature plates of 280C under a pressure of 5 MPa for 10 min was applied to compress specimens. Then cooled them in water and ice bath to achieve transparent films. The influence of different amount of nanoclay addition on resultant nanocmposites was studied by Fourier transform infrared spectroscopy (FT-IR) and mechanical test. Also, influence of nanoclay presence on water vapor permeability (WVP), color and transparency of the nanocomposites were investigated. Results & Discussion: The results showed that nanoclay addition improved the mechanical properties (Young’s modulus, elongation at break and tensile strength) and WVP up to 3% (wt). However, nanoclay addition reduced the transparency of resultant nanocomposites films but it prevented wave transmission at three UV region which leads to better protective effect of film as a food packaging materials. It seems that introduction of Cloisite 15A into the PET matrix reinforced the mechanical properties of resultant nanocomposites. The Young’s modulus of the nanocompo-sites significantly increased compared with the neat PET, indicating that PET/Cloisite 15A nanocomposites were stiffer than PET. The maximum Young’s modulus was observed for PET/C15A containing 3% wt with an increment about 8 MPa. This increase in modulus may be attributed to uniform dispersion and alignment of nanoclay along with compatibil-ity with PET matrix as confirmed by XRD, DSC and SEM. The Young’s modulus enhancement is consistent with that of other research (KIMet al. 2007; Scaffaroet al. 2011; Ghanbari et al. 2013a,b]. Tensile strength like elongation at break shows same trend, increases on increasing nanoclay content except for nanocomposite containing 5% which indicates brittle behavior compared to PET. This can be explained consider-ing that higher aspect ratio of nanoclay tends to aggregate and forms tactoids (as shown in SEM and XRD) and conse-quently indicates poor mechanical properties.
Leila Abolghasemi Fakhri; Babak Ghanbarzadeh; Jalal Dehghan nia; Ali Akbar Entezami
Abstract
The high hydrophilic property of biopolymer based plastics is one of the most important defects of them. Blending biopolymers with compatible synthetic polymers and using nano particles such as nanoclay as nanofiller are improving methods that have been extensively considered in recent years. Carboxymethyl ...
Read More
The high hydrophilic property of biopolymer based plastics is one of the most important defects of them. Blending biopolymers with compatible synthetic polymers and using nano particles such as nanoclay as nanofiller are improving methods that have been extensively considered in recent years. Carboxymethyl cellulose (CMC) is one of the lowest cost biopolymers that have enormous applications in different industries and polyvinyl alcohol (PVA) is a synthetic polymer which has a high compatibility with biopolymers. In this research, CMC-PVA nanocomposites containing 3-10% Montmorillonite (W/W CMC) were prepared by casting method. The X-ray diffraction (XRD) results indicated the formation of an exfoliated nanostructure in all MMT content samples. Nanocomposites containing 10% MMT exhibited 29.06% reduction in water vapor permeability (WVP) compared to the blend film without nanoclay. Samples with 10% MMT, showed the lowest surface hydrophilisity (contact angle = 65.1o). The differential scanning calorimetry (DSC) results indicate that by increasing of MMT contents, the glass transition disappeared gradually and no glass transition was observed in the thermograms of the films containing 5, 7 and 10% MMT.
Babak Ghanbarzadeh; Ali Akbar Entezami
Abstract
The starch based films have some disadvantages such as weak mechanical and poor water barrier properties that restrict their applications in food packaging. In the present research, the polyvinyl alcohol (POVH), as a compatible polymer, and montmorillonite (MMT) nanoclay, as a nanofiller, were added ...
Read More
The starch based films have some disadvantages such as weak mechanical and poor water barrier properties that restrict their applications in food packaging. In the present research, the polyvinyl alcohol (POVH), as a compatible polymer, and montmorillonite (MMT) nanoclay, as a nanofiller, were added to plasticized starch film (PS) to improve its properties and also to produce PS-MMT-PVOH nanocomposits with different MMT content (3,5,7%). The results of X-ray diffraction (XRD) villustrated that the nanostructure of investigated starch based nanocomposites films has an exfoliated structure which can be attributed to the good dispersing of filler in polymer matrix. DSC results showed that with adding MMT and increasing its content from 0 to 7%, melting point and Tg increased from 242ᵒC to 262ᵒC and 148ᵒC to 188ᵒC. The results of tensile test showed that addition of PVOH and MMT increased the ultimate tensile strength (UTS) and decreased the water vapor permeability (WVP) of nanocomposite films.
