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Starches plasticized with glycerol/citric acid/stearic acid and tributyl 2-acetylcitrate (ATBC), respectively, were processed with poly (butylene adipate-Co-terephthalate (PBAT) via extrusion and a film-blown process. All the composite films were determined for morphology, mechanical, thermal stability, crystalline, and optical properties. Results show that the most improved morphology was in the 30% glycerol plasticized PBAT/thermoplastic starch (TPS) composite films, characterized by the smallest and narrowest distribution of TPS particle sizes and a more uniform dispersion of TPS particles. However, the water absorption of PBAT/TPS composite films plasticized with glycerol surpassed that observed with ATBC as a plasticizer. Mechanical properties indicated insufficient plasticization of the starch crystal structure when using 10% ATBC, 20% ATBC, and 20% glycerol as plasticizers, leading to poor compatibility between PBAT and TPS. This resulted in stress concentration points under external forces, adversely affecting the mechanical properties of the composites. All PBAT/TPS composite films exhibited a negative impact on the initial thermal decomposition temperature compared to PBAT. Additionally, the haze value of PBAT/TPS composite films exceeded 96%, while pure PBAT had a haze value of 47.42%. Films plasticized with 10% ATBC, 20% ATBC, and 20% glycerol displayed lower transmittance values in the visible light region. The increased transmittance of films plasticized with 30% glycerol further demonstrated their superior plasticizing effect compared to other PBAT/TPS composite films. This study provides a simple and feasible method for preparing low-cost PBAT composites, and their extensions are expected to further replace general-purpose plastics in daily applications.

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Wood-polymer composites (WPCs) are a class of materials intensively studied and promoted in the context of sustainable development, mainly when aspects related to the increasing awareness of environmental issues and waste management are considered. Feasible opportunities for producing WPCs with value-added properties intended for common applications emerge when polymers, either synthetic or from renewable resources, raw or waste, are employed in re-/up-cycling approaches. In this context, some examples of easily achievable WPCs are presented herein, namely, formulations based on different wood waste and polymer matrices (synthetic: polypropylene and malleated polypropylene as a compatibilizer; natural: plasticized starch). Their level of performance was assessed through different characterization methods (FTIR, WAXD, TGA, DSC, mechanical test, etc.). The benefits and limitations of this approach are also discussed.

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Plasticized starch (PLS) nanocomposite films using glycerol and reinforced with graphene (G) and graphene oxide (GO) were prepared by solvent casting procedure. On one hand, the influence of adding different G contents into the PLS matrix was analyzed. In order to improve the stability of G nanoflakes in water, Salvia extracts were added as surfactants. The resulting nanocomposites presented improved mechanical properties. A maximum increase of 287 % in Young's modulus and 57 % in tensile strength was achieved for nanocomposites with 5 wt% of G. However, it seemed that Salvia acted as co-plasticizer for the PLS. Moreover, the addition of the highest G content led to an improvement of the electrical conductivity close to 5 × 10-6 S/m compared to the matrix. On the other hand, GO was also incorporated as nanofiller to prepare nanocomposites. Thus, the effect of increasing the GO content in the final behavior of the PLS nanocomposites was evaluated. The characterization of GO containing PLS nanocomposites showed that strong starch/GO interactions and a good dispersion of the nanofiller were achieved. Moreover, the acidic treatment applied for the reduction of the GO was found to be effective, since the electrical conductivity was 150 times bigger than its G containing counterpart.

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Composites based on natural rubber and plasticized starch obtained by the conventional method of sulfur cross-linking using four types of vulcanization accelerators (Diphenyl guanidine, 2-Mercaptobenzothiazole, N-Cyclohexyl-2-benzothiazole sulfenamide, and Tetramethylthiuram disulfide) were irradiated with an electron beam in the dose range of 150 and 450 kGy for the purpose of degradation. The vulcanization accelerators were used in different percentages and combinations, resulting in four mixtures with different potential during the cross-linking process (synergistic, activator, or additive). The resulting composites were investigated before and after irradiation in order to establish a connection between the type of accelerator mixture, irradiation dose, and composite properties (gel fraction, cross-linking degree, water absorption, mass loss in water and toluene, mechanical properties, and structural and morphological properties). The results showed that the mixtures became sensitive at the irradiation dose of 300 kGy and at the irradiation dose of 450 kGy, and the consequences of the degradation processes were discussed.

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Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of applications, such as packaging. Herein, the effect of the processing (i.e., starch gelatinization, addition of glycerol as plasticizer, casting to obtain films) and of the sepiolite filler amount on the microstructure of starch-based nanocomposites was investigated by SS-NMR (solid-state nuclear magnetic resonance), XRD (X-ray diffraction) and FTIR (Fourier-transform infrared) spectroscopy. Morphology, transparency and thermal stability were then assessed by SEM (scanning electron microscope), TGA (thermogravimetric analysis) and UV-visible spectroscopy. It was demonstrated that the processing method allowed to disrupt the rigid lattice structure of semicrystalline starch and thus obtain amorphous flexible films, with high transparency and good thermal resistance. Moreover, the microstructure of the bio-nanocomposites was found to intrinsically depend on complex interactions among sepiolite, glycerol and starch chains, which are also supposed to affect the final properties of the starch-sepiolite composite materials.

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In this work, nanocomposite hydrogels were prepared by gamma-radiation copolymerization of acrylic acid (AAc) onto plasticized starch (PLST)/montmorillonite clay (MMT)/chitosan (CS) blends. The effect of irradiation dose and MMT nanoparticle contents on the gel fraction and water absorption characters of PAAc-co-(PLST/MMT/CS) hydrogels was investigated. In addition, the structure-property behavior of the nanocomposite hydrogels was characterized by FTIR spectroscopy, thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The study showed that the appropriate dose of gamma irradiation to achieve homogeneous nanocomposite hydrogels films and the highest absorption in water was 15 kGy, regardless of composition. The introduction of MMT up to 5-wt (%) improved the physical properties and enhanced the drug uptake-release characters. The effect of the nanocomposite hydrogels on skin wound healing were evaluated by rat models, taking sulfanilamide as a model drug. The profiles of rat skin after different time intervals up 21 days revealed that wounds treated with the copolymer hydrogels were healed faster which it may considered as a potential candidate for wound dressing materials.

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Rubber-based wastes represent challenges facing the global community. Human health protection and preservation of environmental quality are strong reasons to find more efficient methods to induce degradation of latex/rubber products in order to replace devulcanization, incineration, or simply storage, and electron beam irradiation is a promising method that can be can be taken into account. Polymeric composites based on natural rubber and plasticized starch in amounts of 10 to 50 phr, obtained by benzoyl peroxide cross-linking, were subjected to 5.5 MeV electron beam irradiation in order to induce degradation, in the dose range of 150 to 450 kGy. A qualitative study was conducted on the kinetics of water absorption in these composites in order to appreciate their degradation degree. The percentages of equilibrium sorption and mass loss after equilibrium sorption were found to be dependent on irradiation dose and amount of plasticized starch. The mechanism of water transport in composites was studied not only through the specific absorption and diffusion parameters but also by the evaluation of the diffusion, intrinsic diffusion, permeation, and absorption coefficients.

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Polymeric composites based on natural rubber (NR) and plasticized starch (PS) obtained by peroxide cross-linking have been subjected to electron beam irradiation in order to investigate their degradation. The amount of PS ranged from 10 to 50 phr and the irradiation dose from 150 to 450 kGy. Irradiation was performed in atmospheric conditions using a linear electron accelerator of 5.5 MeV. Changes in chemical, physical, structural, and morphological properties of composites were correlated with variables, such as PS loading and irradiation dose. Thus, mechanical properties, gel fraction, cross-linking degree, water uptake, weight loss in toluene/water were compared with those obtained before irradiation. The changes in structure and morphology were studied by Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. Both PS loading and irradiation dose were found to be responsible for the degradation installing. Moreover, it has been shown that at the dose of 450 kGy, chain scission is dominant over cross-linking.

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The obtaining and characterization of some environmental-friendly composites that are based on natural rubber and plasticized starch, as filler, are presented. These were obtained by peroxide cross-linking in the presence of a polyfunctional monomer used here as cross-linking co-agent, trimethylolpropane trimethacrylate. The influence of plasticized starch amount on the composites physical and mechanical characteristics, gel fraction and cross-link density, water uptake, structure and morphology before and after accelerated (thermal) degradation, and natural (for one year in temperate climate) ageing, was studied. Differences of two orders of magnitude between the degradation/aging methods were registered in the case of some mechanical characteristics, by increasing the plasticized starch amount. The cross-link density, water uptake and mass loss were also significant affected by the plasticized starch amount increasing and exposing for one year to natural ageing in temperate climate. Based on the results of Fourier Transform Infrared Spectroscopy (FTIR) and cross-link density measurements, reaction mechanisms attributed to degradation induced by accelerated and natural ageing were done. SEM micrographs have confirmed in addition that by incorporating a quantity of hydrophilic starch amount over 20 phr and by exposing the composites to natural ageing, and then degradability can be enhanced by comparing with thermal degradation.

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Nano-biocomposites based on halloysite nanoclay and potato starch were elaborated by melt blending with different polyol plasticizers such as glycerol, sorbitol or a mixture of both. The effects of the type of plasticizer and clay content on potato starch/halloysite nano-biocomposites were studied. SEM analyses combined with ATR-FTIR results showed that a high content of sorbitol had a negative effect on the dispersion of the halloysite nanoclay in the starchy matrix. XRD results demonstrated that incorporation of halloysite nanoclay into glycerol-plasticized starch systems clearly led to the formation of a new crystalline structure. The addition of halloysite nanoclay improved the thermal stability and decreased the moisture absorption of the nano-biocomposites, whatever the type of plasticizer used. Halloysite addition led to more pronounced improvement in mechanical properties for glycerol plasticized system compared to nanocomposites based on sorbitol and glycerol/sorbitol systems with a 47% increase in tensile strength for glycerol-plasticized starch compared to 10.5% and 11% for sorbitol and glycerol/sorbitol systems, respectively. The use of a mixture of polyols was found to be a promising way to optimize the mechanical properties of these starch-based nanocomposites.

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A solution mixing and ultrasonic dispersion method as a green, the fast, inexpensive and effective technique was utilized to prepare glycerol plasticized-starch (GPS)/ascorbic acid (AA)-MWCNTs nanocomposites (NCs) via the introduction of various amounts of AA-MWCNTs (3, 6 and 9wt%) as filler into GPS matrix. The GPS was synthesized by addition of glycerol (50%) as a plasticizer to starch which enhances its flexibility. Characterization of the obtained GPS/AA-MWCNTs NCs was accomplished by different techniques. The optimum filler content for the generation of fine electrical conductivity and good mechanical properties was found to be about 3wt%. The distribution of AA-MWCNTs at the low content (3wt%) in the GPS matrix was better due to the strong linkage between nanofiller and GPS in GPS/AA-MWCNTs NC. The results of adsorption studies showed that the fabricated NC can be a good adsorbent for removal of methylene blue (MB) dye from aqueous solutions.

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Starch was combined with plasticizers such as glycerol, sorbitol, glycerol/sorbitol and urea/ethanolamine blends by means of high shear extrusion process to prepare thermoplastic starch (TPS). Effect of storage time and plasticizers on the structural stability of melt processed TPS was investigated. Morphological observation, X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy reveal that melt extrusion process is efficient in transforming granular starch into a plasticized starch for all plasticizer compositions. XRD analysis highlights major changes in the microstructure of plasticized starch, and dependence of crystalline type and degree of crystallinity mainly on the plasticizer composition and storage time. Dynamical mechanical analysis (DMA) yields a decrease of the peak intensity of loss factor with aging time. The effect of ageing on tensile strength also appears to be highly dependent on the plasticizer composition. Thus, through different plasticizer combinations and ageing, starch-based materials with significant differences in tensile properties can be obtained, which may be tuned to meet the requirements of a wide range of applications.

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The aim of this paper is to understand the influence of plasticizer and plasticizer amount on the mechanical and deformation behaviors of plasticized starch. Glycerol, sorbitol and mannitol have been used as plasticizers. After extrusion of the various samples, dynamic mechanical analyses and video-controlled tensile tests have been performed. It was found that the nature of plasticizer, its amount as well as the aging of the material has an impact on the involved deformation mechanism. The variations of volume deformation could be explained by an antiplasticization effect (low plasticizer amount), a phase-separation phenomenon (excess of plasticizer) and/or by the retrogradation of starch.

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A comparative performance study of cellulose whiskers (CW) and starch nanoparticles (SN) on plasticized starch (PS) reinforcement has been presented. In order to study the involved surface phenomena, CW and SN were extracted through acid hydrolysis using sulfuric acid to fulfill the similar surface groups and interactions. CW-filled and SN-filled nanocomposites were then prepared with relatively identical process to alleviate the effect of fabrication method for better comparison of CW and SN performance on PS reinforcement. Morphology of nanoparticles and their dispersion state in the corresponding nanocomposites were investigated by transmission electron microscopy and field emission scanning electron microscopy, respectively. X-ray diffraction was used for crystallography of nanocomposites and established the transcrystallization only in CW-filled nanocomposites. Nanocomposites comprising quasi-spherical SNs showed higher reinforcement in dynamic mechanical tests compared to the corresponding nanocomposites containing rod-like CWs, which were attributed to more efficient filler/filler and filler/matrix interactions originated from hydrogen bonding in SN-filled nanocomposites.

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Films of thermoplastic starch (TPS) plasticized with different contents of urea were prepared by using a solution casting method. Scanning electron microscopy, X-ray diffraction and IR spectroscopy were used to characterize structures of the TPS films, respectively. Water vapor sorption isotherms and tensile properties of the films were determined. TPS films showed more smooth and transparent in appearance and less B-type crystallinity than the starch film without urea. The effect of urea content on the structure and behavior of the TPS film could be divided in three stages: (1) below urea 10% where urea interacted with starch via H-bonding and the films showed an antiplasticization effect, (2) from urea 10% to 30% where an apparent plasticization effect appeared on the starch because of free urea molecules as the effective plasticizer, and (3) a macroscopic phase separation occurred due to supersaturation of urea when urea content was more than 30%.

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