Thermoplastic Starch Films Research Articles

Optimizing Thermoplastic Starch Film with Heteroscedastic Gaussian Processes in Bayesian Experimental Design Framework.

The development of thermoplastic starch (TPS) films is crucial for fabricating sustainable and compostable plastics with desirable mechanical properties. However, traditional design of experiments (DOE) methods used in TPS development are often inefficient. They require extensive time and resources while frequently failing to identify optimal material formulations. As an alternative, adaptive experimental design methods based on Bayesian optimization (BO) principles have been recently proposed to streamline material development by iteratively refining experiments based on prior results. However, most implementations are not suited to manage the heteroscedastic noise inherently present in physical experiments. This work introduces a heteroscedastic Gaussian process (HGP) model within the BO framework to account for varying levels of uncertainty in the data, improve the accuracy of the predictions, and increase the overall experimental efficiency. The aim is to find the optimal TPS film composition that maximizes its elongation at break and tensile strength. To demonstrate the effectiveness of this approach, TPS films were prepared by mixing potato starch, distilled water, glycerol as a plasticizer, and acetic acid as a catalyst. After gelation, the mixture was degassed via centrifugation and molded into films, which were dried at room temperature. Tensile tests were conducted according to ASTM D638 standards. After five iterations and 30 experiments, the films containing 4.5 wt% plasticizer and 2.0 wt% starch exhibited the highest elongation at break (M = 96.7%, SD = 5.6%), while the films with 0.5 wt% plasticizer and 7.0 wt% starch demonstrated the highest tensile strength (M = 2.77 MPa, SD = 1.54 MPa). These results demonstrate the potential of the HGP model within a BO framework to improve material development efficiency and performance in TPS film and other potential material formulations.

Starch-calcium inclusion complexes: Optimizing transparency, anti-fogging, and fluorescence in thermoplastic starch

With the increasing demand for anti-fogging transparent material and environmental concern, developing sustainable intrinsically hydrophilic and anti-fogging thermoplastic material is important. In this work, thermoplastic starch (TPS) films with good anti-fogging and optical properties were prepared via coordinative interactions with calcium chloride (CaCl2), zinc chloride (ZnCl2) and magnesium chloride (MgCl2). Among them, TPS with the incorporation of CaCl2 exhibited excellent anti-fogging and high optical transparency. Notably, the haze of TPS-0.2Ca just increased from 2.5 % to 3.8 %, with transparency remaining robust at 80 %. FTIR, XPS and 2D-WAXD results demonstrated the formation of inclusion complexes between Ca2+ and hydroxyl groups, which could modulate the hydrophobicity and hydrophilicity of TPS. Moreover, DMA, POM, and AFM results revealed that the formation of starch-calcium inclusion complex was crucial for achieving uniform intensity distribution, reduced crystalline areas, minimized light scattering, and decreased surface roughness, thereby contributing to the high transparency and low haze of TPS-Ca. Furthermore, TPS-Ca samples exhibited inherent fluorescent properties under UV light, showing the potential as disposable and eco-friendly fluorescence materials. This work provides new insights into design of sustainable TPS-based materials that combine robust antifogging performance with advanced optical property.

Biodegradation of thermoplastic starch by a newly isolated active microbial community: Deciphering the biochemical mechanisms controlling bioprocess robustness

Defining sustainable end-of-life routes for bioplastics comprises a task of outmost importance, while biological recycling constitutes the most favorable option for several biopolymers, such as thermoplastic starch (TPS). To our knowledge, this is the first study to assess the biodegradation of TPS pellets and films in aqueous cultures employing an acclimated microbial community. Biological treatment of bioplastics displayed a two-phase pattern that included different biodegradation rates, where TPS removal in the first phase remained high and decelerated in the second phase reaching a plateau. Thus, TPS weight reduction of 14.8 % was observed using pellets following 10 d of incubation, while although films exhibited higher reduction (slightly over 30 % in 15 d), the biodegradation rate was significantly reduced thereafter. Several changes of starch related bands were detected (using FTIR) in the surface of both pellets and films during the bioprocess, indicating induction of a common biodegradation pathway. Distinct bacterial assemblages were formed during the TPS biodegradation process and statistically significant differences were detected in the abundance of several genera between the two degradation phases. Fungal communities were more stable (Fusarium and Neocosmospora were dominant at all times) and there was no effect of biofilm or degradation phase on fungal community composition. Overall, a more diverse community incorporating lower catalytic activity was gradually formed, as confirmed by the shift between k-stategist and r-stategist taxa monitored, while crystalline over amorphous regions were enhanced in the biopolymer during TPS biodegradation, responses consistent with the biodegradation rate reduction observed in the plateau stage. The study highlighted the biochemical mechanism limiting TPS biodegradation processes and the significant potential of the newly isolated community in the development of TPS waste treatment technologies.

ScCO2-processed thermoplastic starch/chitosan oligosaccharide blown films and their oxygen barrier or antibacterial applications

Abstract Antibacterial and oxygen barrier films were inventively prepared by blending very small loadings (<2 wt%) of chitosan oligosaccharide (COS) or chitosan (CS) in thermoplastic starch (TPS) and/or processing with supercritical carbon dioxide (scCO2). Oxygen transmission rates (OTR) and free-volume-hole (FVH) characteristics of scCO2-processed TPS/COS and TPS/CS blown films diminish to a minimum, as their COS or CS approach a specific compatibility limit content. The minimum OTR and FVH characteristics of scCO2-processed TPS/COS films are somewhat smaller than those of corresponding TPS/COS films without scCO2-assistance, and decrease further with decreasing COS molecular weights. The minimum OTR values of scCO2-processed TPS/COS blown films with COS’s molecular weight of 200 and 500 are only 4.1 and 4.5 cm3/m2 × day × atm, respectively, and their antibacterial rates of Staphylococcus aureus are ≥97 %, which make them as promising antibacterial and oxygen barrier films having OTR ≦ 5 cm3/m2 × day × atm. Among other things, longitudinal or transversal tensile strengths acquired for the properly scCO2-processed TPS/COS or TPS/CS films are ∼30 to ∼50 % higher than those of the TPS films. Dynamic mechanical relaxation results of these scCO2-processed reveal that chitosan oligosaccharide or chitosan are compatible with TPS, as COS or CS contents are ≤ the compatibility limit value.

Enhancing the electrochemical properties of biopolymer composites using starch‐graphene nanoplatelets

AbstractThe study presents the ideal distribution of graphene nanoplatelets (GNP) within the thermoplastic starch (TPS) matrix significantly elevated the thermal and electrical conductivities, as well as the electrochemical efficiency of the biocomposites. Additionally, the incorporation of GNP resulted in an increased thermal stability for the TPS, as indicated by the elevated temperatures required for maximum degradation. The biocomposites exhibited a self‐aligned layered structure, creating conductive pathways and enhancing electron conduction. An electrical conductivity increased as the concentration of GNP increased, with the highest conductivity observed on the top and bottom surface with the value of 4.23 × 10−7 S/m and 3.92 × 10−6 S/m when 12 wt% of GNP was added. The presence of hydroxyl groups in TPS facilitated the formation of hydrogen bonds with GNP, preventing GNP from stacking and forming a more uniform conductive network within the film. The addition of 15 wt% GNP also improved the capacitive performance of the TPS matrix, as evidenced by higher current responses and larger quasi‐rectangular areas in the cyclic voltammetry curves compared to neat TPS. The Nyquist plots which are illustrated impedance data showed that the TPS film with 12 wt% GNP exhibits the smallest semicircle, indicating the highest conductivity which is suggested that GNP improves charge transfer compared to pure TPS.Highlights Optimal dispersion of GNP enhanced the biocomposite's properties. The electrical conductivity increases with the GNP content until 12 wt%. TPS/GNP self‐aligned layered improved conduction and capacitive behavior. GNP improved thermal stability by restricting polymer chain movement. Electrochemical impedance shows improved properties of TPS/GNP.

Poly(butylene adipate-co-terephthalate)/thermoplastic canna starch (Canna edulis ker.) (PBAT/TPS) blend film – A novel biodegradable material

The PBAT (poly (butylene adipate-co-terephthalate) is a promising biodegradable material. However, it is often blend with hydrophilic polymers since its degradation rate in the aquatic environment is still limited. In this study, the blend PBAT/TPS (thermoplastic starch) films, namely BFs, were prepared by a blow extrusion approach, and evaluated for hydrolysis in four studied mediums acid (HCl, 1 M, 2 M, and 3 M), alkaline (NaOH, pH = 9, 11, and 13), phosphate buffer (pH = 7.4), and artificial seawater. The hydrolyzed BFs were characterized by weight loss, mechanical properties, scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and differential scanning calorimetry (DSC). A larger starch content in the BFs caused hydrolysis more quickly. The highest hydrolytic rate was found in the alkaline solution, followed by the acid medium. The complete abiotic hydrolysis of the BFs was 3 M HCl for 14 days or NaOH (pH 13) for 35 days. After 180 days of incubation, the film containing 70.5 % PBAT/TPS granules has been associated with the highest biodegradation rate of 76.31 % in composting.

Preparation and properties of poly[(butylene adipate)‐co‐terephthalate]/thermoplastic hydroxypropyl starch films

AbstractPoly[(butylene adipate)‐co‐terephthalate] (PBAT) is currently the most widely used and versatile petroleum‐based fully biodegradable polyester, drawing extensive attention from researchers. However, the high production cost of PBAT restricts its widespread application. Currently, incorporating fillers into PBAT materials is considered the most effective approach to reduce production costs, with thermoplastic starch recognized as the optimal filler for PBAT base materials. Nevertheless, the low mechanical strength of thermoplastic starch significantly compromises the performance of PBAT base materials. In this study, thermoplastic starch with higher mechanical strength was prepared by partially substituting commonly used glycerol with a higher molecular weight sorbitol as the plasticizer. The enhanced thermoplastic starch was then used as a filler for PBAT materials, leading to the fabrication of PBAT‐based blend films with high starch content. Mechanical property tests revealed a 52.2% and 65.3% increase of tensile strength in the transverse and longitudinal directions, respectively, when sorbitol partially replaced glycerol as the plasticizer for thermoplastic starch. Scanning electron microscopy results demonstrated improved dispersion of thermoplastic starch particles in PBAT when sorbitol and glycerol were used together. Meanwhile, the thermal performance and stability of PBAT were not significantly affected by the thermoplastic starch filling. © 2024 Society of Chemical Industry.

Influence of Choline Chloride/Urea and Glycerol Plasticizers on the Mechanical Properties of Thermoplastic Starch Plastics.

Bio-based plastics made of food-safe compostable materials, such as thermoplastic starch (TPS), can be designed into films that have potential to replace many non-biodegradable single-use plastic (SUP) items. TPS film characteristics, such as elongation at break and tensile strength, are largely affected by the choice of the plasticizers used in formulation. Our work identifies the mechanical properties and the chemical structural differences between TPS films made with two different plasticizer mixtures that have not yet been compared alongside one another: deep eutectic solvent choline chloride/urea (1:2) (CC:U) and glycerol with an acetic acid catalyst (AA:G). Potato-based TPS samples were formed by mixing each plasticizer with a consistent amount of potato starch and distilled water with heat. After gelation formation, the viscous TPS mixture was centrifuged to degas and extruded. Films were dried at controlled room temperature. Characterization included the tensile testing of coupons according to ASTM (American Society of Testing and Materials) standard D638, attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), melting point (MP), and scanning electron microscopy (SEM). The AA:G films displayed significantly higher tensile strength (M = 2.04 ± 1.24 MPa) than the CC:U films (M = 0.18 ± 0.08 MPa); however, the CC:U films had higher elongation at break (M = 47.2 ± 3.6%) than the AA:G films (M = 31.1 ± 12.6%). This can be explained by the difference in functional groups, composition, and the degree of crystallinity evidenced by the FTIR, XRD, MP, and SEM results. Our findings suggest that potato-based TPS films with an AA:G plasticizer mixture hold promise for SUP applications that require more strength, while CC:U films may be more suited for wraps and bags that require flexibility. These innovations can aid to mitigate the environmental impact of harmful plastic waste.

Evaluation of effect of boric acid on thermoplastic starch: Morphological, mechanical, barrier, and optical properties

AbstractIn this study, starch was modified with different amounts of boric acid, and the degree of substitution of the synthesized compounds at different temperatures and times was determined by Fourier transform infrared (FTIR) and titration methods. The degrees of substitution in both methods showed similar tendency. Optimum conditions were determined, and thermoplastic starch (TPS) and boric acid (B) films were prepared by casting method using glycerol as plasticizer. The morphological properties of the films were studied by scanning electron microscope‐energy dispersive spectrometry (SEM‐EDS). According to the FTIR results, it was observed that the BO and BOC stretching vibrations increased when the amount of boric acid increased. The tensile strength, water barrier (swelling capacity, solubility, and water vapor permeability), and optical properties of samples were investigated. The swelling capacity, solubility, and water vapor permeability of the films decreased with the addition of 0.5% boric acid to the starch, but the highest tensile strength was achieved. The tensile strength for TPSB0.5% increased compared to control group TPS. In addition, the film showed the highest transparency. Thermoplastic film containing 0.5% boric acid can be used as a packaging material due to its improved mechanical and water barrier.Highlights The thermoplastic starch and boric acid composite were successfully produced. The presence of boric acid was confirmed by energy dispersive spectrometry (EDS). The degree of substitution was determined by two different methods. Transparency increased with the addition of boric acid. Tensile strength improved with boric acid content.

Evaluation of physicochemical properties of citric acid crosslinked starch elastomers reinforced with silicon dioxide.

Thermoplastic starch (TPS), derived from renewable resources, offers advantages such as biodegradability and lower production costs compared to petroleum-based plastics. However, its limited mechanical properties pose a challenge for broader applications. This research aims to explore the potential of enhancing the mechanical and barrier properties of TPS films through the incorporation of silicon dioxide as a reinforcement filler and citric acid as a crosslinking agent. By introducing silicon dioxide as a reinforcement filler, the mechanical strength of the TPS films is expected to be improved. Additionally, the incorporation of citric acid as a crosslinking agent is anticipated to enhance the barrier properties of the films. The combination of these additives holds promise for creating TPS films with improved performance, contributing to the development of sustainable and environmentally friendly materials in various industries. The results reveal that SiO2 improves the stiffness of the films at lower concentrations but causes brittleness at higher concentrations. In contrast, citric acid crosslinked films exhibit improved flexibility and density. Scanning electron microscopy demonstrates the morphological changes in the films, with SiO2 affecting surface roughness and aggregate formation. SiO2 reduces film thickness and transparency, while citric acid enhances water resistance and barrier properties. X-ray diffraction analysis shows a reduction in crystallinity due to the plasticization process. Fourier-transform infrared spectroscopy highlights chemical changes and antimicrobial activity is observed with citric acid against specific bacteria. The soil burial test reveals that citric acid crosslinked films exhibit slower degradation due to antimicrobial properties. The combination of SiO2 reinforcement and citric acid crosslinking enhances the overall performance of the films, promising sustainable and environmentally friendly materials for various applications.

Influence of Epilobium parviflorum Herbal Extract on Physicochemical Properties of Thermoplastic Starch Films.

In this study, for the first time, Epilobium parviflorum Schreb. (E, hoary willowherb) aqueous extract was introduced into edible biopolymer films and its influence on physicochemical properties of the final products were investigated. Potato starch was gelatinized in the herbal tea to obtain thermoplastic starch (TPS) films via the casting method. The characterization of the films included mechanical, antioxidative, water (WVTR, contact angle, swelling degree) and UV radiation barrier properties as well as microstructure analysis (SEM). Obtained results indicated that the presence of the extract (rich in phenolic compounds) in the films acted as a co-plasticizer for starch and led to a higher elongation at break, up to 70%, with a parallel increase in tensile strength up to ca. 9 MPa. Moreover, TPS films with E exhibited lower WVTR values and absorption of UV light in comparison with the control TPS film. DPPH scavenging activity of TPS E films immersed in methanol was ca. 92%, and it was related to the release of the extract into liquid media. Novel TPS E films are characterized by multifunctional properties that can be used, e.g., in the active packaging sector.

STUDY OF THE EFFECTIVENESS OF THE INFLUENCE OF PLASTICIZERS AND FUNCTIONAL ADDITIVES IN THE RECEIVING OF THERMOPLASTIC STARCH ON ITS FILM-FORMING AND DESTRUCTIVE PROPERTIES

A literature review on the production of thermoplastic starch (TPS) with various plasticizing additives as a component of biodegradable polymer compositions was conducted. Plasticizing additives with different functional groups, due to which starch modification occurs, were analyzed. In order to expand the spectrum of functional additives for the formation of TPS, the introduction of acids with different amounts of carboxyl groups: citric, oxalic, oleic, stearic was studied. The technological parameters of thermomechanical processing of starch compositions and the quantitative composition of the components are determined. Physical and mechanical tests of strength and elasticity of film samples of TPS compositions and compatible with synthetic polymer were carried out. In order to obtain the structural characteristics of TPS and TPS films with polyethylene, studies were carried out by IR-Fourier spectroscopy and mass spectrometry. Studies of the effect of UV irradiation on the degradability of TPS compositions after exposure in a climate chamber for 90 days were conducted. It was found that the loss of strength and elasticity of TPS and TPS+PE film samples is (82–90)%, elasticity (60–70)%, depending on plasticizing and structure-forming additives and their amounts.

Renewable thermoplastic starch/sugar alcohol blends and their oxygen barrier application

AbstractFully renewable oxygen barrier thermoplastic starch (TPS)/sugar alcohol blown films were innovatively prepared by blending proper loadings of Erythritol (ET), Sorbitol (ST), and Lactitol (LT) and supercritical carbon dioxide (scCO2) assistance. The oxygen transmission rate (OTR) values of the properly prepared scCO2TPSxETy, scCO2TPSxSTy, and scCO2TPSxLTy films reduced to 4.3, 6.6, and 12.5 cm3/m2∙day∙atm, which are about 5–28 times smaller than those of the conventional TPS films reported in the literature. The free‐volume‐cavity characteristics (FVCC) and OTR detected for TPSxETy (or scCO2TPSxETy), TPSxSTy (or scCO2TPSxSTy), and TPSxLTy (or scCO2TPSxLTy) films diminished to a minimum, as their ET, ST and LT loadings came near an optimal value. Slightly smaller OTR and FVCC values were detected for scCO2TPSxETy, scCO2TPSxSTy, and scCO2TPSxLTy films than those of corresponding TPSxETy, TPSxSTy, and TPSxLTy films prepared without scCO2‐assistance. The smallest OTR and FVCC detected for the properly prepared TPSxETy (or scCO2TPSxETy), TPSxSTy (or scCO2TPSxSTy), and TPSxLTy (or scCO2TPSxLTy) films diminished with decreasing sugar alcohol's molecular weight. An essential result is that the OTR of the properly prepared scCO2TPSxETy film was merely 4.3 cm3/m2∙day∙atm, which is small enough to meet the demand of high oxygen barrier packaging application. Dynamic molecular relaxations detected for these films disclosed that ET, ST, and LT were compatible with TPS, as their loads were ≤ the optimum value. The distinctly reduced OTR and FVCC for these properly prepared films are partially attributed to the reinforced molecular interactions between sugar alcohol and TPS's hydroxyl groups when they were prepared with scCO2‐assistance, optimal sugar alcohol loading, and/or smaller sugar alcohol's molecular weight.Highlights High oxygen barrier thermoplastic starch/sugar alcohol blown films were prepared. The lowest oxygen transmission rate of the renewable film was 4.3 cm3/m2∙day∙atm. This oxygen transmission rate is qualified for high oxygen barrier application. Boosted oxygen barrier property was ascribed to the reduced free volume values.

Effect of super critical carbon dioxide and alkali treatment on oxygen barrier properties of thermoplastic starch/poly(vinyl alcohol) films

Abstract Sustainable oxygen barrier thermoplastic starch (TPS)/polyvinyl alcohol (PVA) blown films were successfully prepared by blending proper PVA loads during NaOH-treating and supercritical carbon dioxide (scCO2) assisted processing. The NaOH-treated TPS or scCO2TPS films showed smaller free-volume-cavity characteristics (FVCC) and oxygen transmission rate (OTR) than those of TPS (or scCO2TPS) prepared without proper alkali-treatment. Smaller OTR and FVCC values were detected for NaOH-treated scCO2TPS films than those of NaOH-treated TPS films prepared without scCO2-assistance. All OTR and FVCC values detected for proper alkali-treated scCO2TPS y PVA z films diminished distinctly to a smallest value, when their PVA loads came near a solubility limit value of 27.5 wt%. An essential result is that the OTR of the optimal NaOH-treated scCO2TPS y PVA z film is merely 3.1 cm3/m2 day atm, which meets the requirement of high oxygen barrier plastics. Dynamic molecular relaxations and WAXD patterns detected for proper NaOH-treated scCO2TPS y PVA z films disclosed that PVA was compatible with TPS, as PVA loads were ≤ the solubility limit value. The distinctly reduced OTR and FVCC detected for optimal NaOH-treated scCO2TPS y PVA z films are partially attributed to the reinforced molecular interactions between hydroxyl groups of TPS and PVA, as they were blended with proper PVA loads during their alkali-treating and scCO2-aid processing.

Flame-retardant phytic acid–decorated thermoplastic starch/halloysite nanotube composite films with enhanced mechanical strength and excellent barrier properties

Thermoplastic starch (TPS), a green and fully biodegradable composite, is considered the most viable option for replacing petroleum-based polymers. However, the poor mechanical properties, high flammability and moisture absorption susceptibility of TPS severely restrict its large-scale applications. Through PA phosphorylation and blending with halloysite nanotubes (HNTs), phytic acid (PA)-phosphorylated HNT/TPS composite films (HNTPSFs) were fabricated with enhanced mechanical strength, excellent flame retardancy, and improved barrier properties. The introduction of HNTs substantially increased the mechanical properties (tensile strength increased 54.3 % and elongation at break decreased 37.0 %) of TPS films and reduced the diffusion of water vapor (decreased 34.1 %). Thermogravimetric analysis studies demonstrated that the HNTPSFs had exceptional thermal stability at their anticipated working temperatures. Furthermore, when the PA content in the composite films increased, the peak heat release rate, total heat release and fire growth index of the HNTPSFs all decreased substantially, demonstrating the improved flame retardancy of HNTPSFs. Hence, the synthesized fully biodegradable TPS composites show enormous potential in the field of renewable biopolymers.

Development and Application of Poly (Lactic Acid)/Poly (Butylene Adipate-Co-Terephthalate)/Thermoplastic Starch Film Containing Salicylic Acid for Banana Preservation.

Bananas are susceptible to the effects of endogenous enzymatic, leading to their rapid decay and deterioration. In order to mitigate economic losses and prolong the shelf life of bananas, the objective of this study was to develop a new and green gas-regulating packaging film. In this study, an active gas-regulating packaging film was prepared by extrusion, with mobil composition of matter (MCM)-41 loaded with salicylic acid (SA) as the active agent and poly (lactic acid) (PLA), poly (butylene adipate-co-terephthalate) (PBAT), and thermoplastic starch (TPS) as the base materials. The obtained films included PLA/PBAT/TPS, PLA/PBAT/TPS-SA, and PLA/PBAT/TPS-MCSA. These films were subsequently applied to banana preservation. The study focused on the variations in soluble solid content (SSC), rate of weight loss (RWL), malondialdehyde (MDA) content, and polyphenol oxidase (PPO) activity of bananas during the preservation process. The results showed that, compared with the PLA/PBAT/TPS film, the oxygen transmission rate of the PLA/PBAT/TPS-MCSA film increased from 384.36 ± 22.06 cm3·m-2·24 h-1·0.1 MPa-1 to 543.10 ± 3.47 cm3·m-2·24 h-1·0.1 MPa-1. Throughout the preservation period, the PLA/PBAT/TPS-MCSA film exhibited superior performance, effectively retarding the increase in banana SSC, RWL, and MDA while inhibiting the elevation of PPO activity and prolonging the shelf life of bananas by 4-5 days. However, this study needs to further investigate the mechanism of function of MCM-41 loaded with SA in banana preservation.

Enhancement of the mechanical properties and water barrier properties of thermoplastic starch nanocomposite films by chitin nanofibers: Biodegradable coating for extending banana shelf life

Starch-based films have limited applications due to their hydrophilicity and poor mechanical performance. Herein, thermoplastic starch (TPS) nanocomposite films with chitin nanofibers (ChNFs) extracted from shrimp-shell waste were successfully fabricated using a solvent casting method. We investigated the effects of the ChNF loadings on the physical, mechanical, and water vapor barrier properties of the nanocomposite films. The well-dispersed ChNFs within the soft matrix associated with the formation of interfacial bonding between ChNFs and starch facilitated the efficient stress transfer from the soft matrix to the stiff ChNFs. Additionally, the presence of ChNFs created tortuous pathways within the films, which could impede the diffusion of water molecules. This resulted in a significant improvement in the mechanical properties, wettability, water resistance, and water vapor barrier properties of the nanocomposites. Compared to the results obtained from the neat TPS films, the TPS nanocomposites reinforced with ChNFs exhibited a 300% higher tensile stress, a 603% Young's modulus, and a considerable increase in the water contact angle, shifting from 86.2° to 98.6°. Furthermore, the ChNF-reinforced nanocomposite films showed no fragmentation after being soaked in water for 12 h under vigorous stirring, whereas the neat TPS films disintegrated under the same conditions. Interestingly, we found that coating a suspension of TPS and ChNFs on bananas effectively delayed their aging, preventing the color change from green to yellow. This promising result demonstrates the potential of the developed coating to extend the shelf life of fresh food produce, reducing food waste and the reliance on single-use petroleum-based packaging.

Use of Raw Peach Gum as a Sustainable Additive for the Development of Water-Sensitive and Biodegradable Thermoplastic Starch Films.

In this study, formulations of thermoplastic starch (TPS) with 5, 10, and 15 parts per hundred resin (phr) of raw peach gum (PG) were prepared by melt extrusion followed by injection molding to obtain standard specimens for characterization. In addition, biodegradable films were developed by compression molding. It was determined that TPS with 5 phr and 10 phr of PG presented similar mechanical behavior to pure TPS after the processing. However, results indicated that adding PG in 10 phr slowed down the starch's retrogradation, delaying the TPS structure's stiffening. Moreover, the TPS-PG formulations presented improved solubility, which increased by 24% with 10 and 15 phr of PG compared to that shown for TPS. Additionally, PG enhanced the compostability of TPS, causing the sample to disintegrate in a shorter period. In conclusion, it was determined that raw PG added in 10 phr could be added as a sustainable additive to modify the biodegradation and water sensitivity of TPS without affecting its mechanical behavior after processing and delaying the retrogradation of the TPS structure, increasing its shelf life.

PREPARATION AND CHARACTERIZATION OF THERMOPLASTIC STARCH FROM PINEAPPLE STEM: EFFECT OF PLASTICIZERS

This work studied the effect of types and amount of plasticizers on thermoplastic starch properties from pineapple stem with good mechanical properties, water resistant and biodegradable. Three plasticizers were studied: erythritol, xylitol, and sorbitol. Thermoplastic starch film was prepared by solution casting. When glycerol was used as co plasticizer, it could improve the flexibility of thermoplastic starch. Thermal properties of thermoplastic starch film by DSC showed that when the plasticizers were added, the heat of fusion (DHm) was reduced. Water absorption of thermoplastic starch films are maximum in 1 hour and constant after immersed in distilled water for 3 hours. Films can maintain in their shapes at least 13 days after that they dissolved. Thermoplastic starch from pineapple stem and plasticizers i.e. sorbitol and xylitol showed no significant difference in water absorption. Thermoplastic starch films from mixed plasticizers showed more hydrophilic when compared with film from single plasticizer. Films without glycerol show high tensile strength and modulus. Thermoplastic starch film from pineapple stem is water resistant and biodegradable in water. All thermoplastic starch degraded within 30 days after biodegradability test in soil. Thermoplastic starch film made from pineapple stem is considered a naturally biodegradable plastic.

Thermoplastic starch hybrid biocomposite films with improved strength and flexibility produced through crosslinking via carboxylic acid

Thermoplastic starch (TPS) suffers from its intrinsic low mechanical strength and high brittleness due to its strong hydrogen bonding and low chain mobility. The conventional way to crosslink the TPS film can improve the strength and stiffness of the films, but usually reduces the flexibility of the film, and increases its brittleness. In this study, the incorporation of the hybrid nanofiller [1 wt% nanocellulose (C) and 4 wt% nano bentonite (B)] into the TPS proved to improve greatly the films’ strength and flexibility. The hybrid nanofillers with ratio 4B:1C was incorporated into the crosslinked thermoplastic corn starch (CR-TPCS) film to increase the its flexibility and toughness and produced a high mechanical strength fully biodegradable film. Two different aqueous carboxylic acids: citric acid (CA) and tartaric acid (TA) with different pH values (2,4,6) as the green crosslinker were employed. Substantial increase of tensile strength (3.98 to 9.17 MPa), Young’s modulus (9.10 to 46.30 MPa) and elongation at break (55.2 to 135.7%) was observed for the CA- 4B1C/pH2 films compared to the CR-TPCS films. The melting temperature (Tm) of the CA-4B1C/pH2 improved compared to the TPCS/4B1C (un-crosslinked) film due to its crosslinking effect. Meanwhile, the CA-4B1C films exhibited the highest degree of substitution and di-esterification with the lowest swelling and water solubility properties due to the formation of a special “bridge” structure between the CA, nanocellulose and plasticizer. The “bridge” structure developed between the TPCS chains serves as the toughener to motivate higher chain stress relaxation and load endurance. The crosslinked “bridge structure” also proved to effectively reduce the retrogradation phenomenal in the TPCS films. This combination method of hybridization and crosslinking is an efficient, low cost, and environmentally friendly technique to overcome the low flexibility and brittleness problem of the TPS based packaging film.