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1.
Int J Biol Macromol ; 264(Pt 2): 130773, 2024 Apr.
Article En | MEDLINE | ID: mdl-38467211

This work reports on the development of starch-rich thermoplastic based formulations produced by using mango kernel flour, avoiding the extraction process of starch from mango kernel to produce these materials. Glycerol, sorbitol and urea at 15 wt% are used as plasticizers to obtain thermoplastic starch (TPS) formulations by extrusion and injection-moulding processes. Mechanical results show that sorbitol and urea allowed to obtain samples with tensile strength and elongation at break higher than the glycerol-plasticized sample, achieving values of 2.9 MPa of tensile strength and 42 % of elongation at break at 53 % RH. These results are supported by field emission scanning electron microscopy (FESEM) micrographs, where a limited concentration of voids was observed in the samples with sorbitol and urea, indicating a better interaction between starch and the plasticizers. Thermogravimetric analysis (TGA) shows that urea and sorbitol increase the thermal stability of TPS in comparison to the glycerol-plasticized sample. Differential scanning calorimetry (DSC) and dynamic-mechanical-thermal analysis (DMTA) verify the increase in stiffness of the sorbitol and urea plasticized TPS and also illustrate an increase in the glass transition temperature of both samples in comparison to the glycerol-plasticized sample. Glass transition temperatures of 45 °C were achieved for the sample with sorbitol.


Mangifera , Plasticizers , Plasticizers/chemistry , Starch/chemistry , Glycerol/chemistry , Flour , Plastics , Sorbitol/chemistry , Urea/chemistry
2.
Polymers (Basel) ; 15(22)2023 Nov 10.
Article En | MEDLINE | ID: mdl-38006105

The mechanical performance of thermoplastic bulk samples obtained by plasticizing wheat flours differing in grain hardness, alveographic parameters, absence or presence of bran, and grinding level was assessed. Grains of four bread wheat (Triticum aestivum L.) cultivars (Altamira, Aubusson, Blasco, and Bologna) were milled with the aim of producing single-cultivar refined flour (R), or wholegrain flour with fine (F) or coarse (C) grinding. The flours were plasticized, injection molded and tested for tensile properties. The results confirmed that the presence of bran increased the strength (σ) and reduced the elongation at break (ε) of thermoplastics obtained from the flours of each cultivar. The grinding level had an effect, since σ was higher and ε was lower in F than in C samples. SEM analysis of samples revealed that the bran and its texture affected the exposure of starch granules to plasticizer. Composting experiments also revealed that the formulations are able to disintegrate within 21 days with a mass loss rate higher in plastics from F than C flours, while germination tests carried out with cress seeds indicated that it takes two months before the compost loses its phytotoxic effects. Overall, the refining and bran particle size of wheat flours, besides their gluten composition and baking properties, represent novel choice factors to be considered when tailoring the manufacturing of plastic materials for selected requirements and uses.

3.
Polymers (Basel) ; 15(18)2023 Sep 17.
Article En | MEDLINE | ID: mdl-37765648

The aim of this work was to develop sustainable patches for wound application, using the biopolymer starch, created using a low-cost 3D printing PAM device. The composition of a starch gel was optimized for PAM extrusion: corn starch 10% w/w, ß-glucan water suspension (filler, 1% w/w), glycerol (plasticizer, 29% w/w), and water 60% w/w. The most suitable 3D printing parameters were optimized as well (nozzle size 0.8 mm, layer height 0.2 mm, infill 100%, volumetric flow rate 3.02 mm3/s, and print speed 15 mm/s). The suitable conditions for post-printing drying were set at 37 °C for 24 h. The obtained patch was homogenous but with low mechanical resistance. To solve this problem, the starch gel was extruded over an alginate support, which, after drying, becomes an integral part of the product, constituting the backing layer of the final formulation. This approach significantly improved the physicochemical and post-printing properties of the final bilayer patch, showing suitable mechanical properties such as elastic modulus (3.80 ± 0.82 MPa), strength (0.92 ± 0.08 MPa), and deformation at break (50 ± 1%). The obtained results suggest the possibility of low-cost production of patches for wound treatment by additive manufacturing technology.

4.
Polymers (Basel) ; 15(4)2023 Feb 20.
Article En | MEDLINE | ID: mdl-36850328

Blending Poly(lactic acid) (PLA) and Poly(ε-caprolactone) (PCL) is a promising strategy to enhance the properties of biodegradable materials. However, these compounds are thermodynamically immiscible and, consequently, compatibilization is required during polymer blending. Reinforced biocomposites can be obtained by adding agricultural wastes generated by industries which are forced to consider waste treatment methods to prevent environmental concerns. Novel PCL/PLA blends were proposed based on the addition of 10 wt.% almond shell (AS) waste combined with 3 wt.% glycidyl methacrylate (GMA) as a compatibilizer. Different PCL-, PLA-, and PCL/PLA-based blends at different percentages (75:25, 50:50, 25:75, 15:85) added with GMA and AS were obtained. The color results highlighted the lower transparency and brownish tone of the studied formulations after the addition of AS. The addition of PCL provided a positive effect on PLA's ductility due to its intrinsically higher flexibility. The combination of GMA and AS improved the mechanical properties of PCL, PLA, and 50:50 controls by reducing yield strength, yield strength at break, and elongation at break values. The 75:25_GMA_AS formulation showed a homogeneous visual appearance, low transparency, and desirable mechanical properties for rigid food packaging applications, reducing the final material cost through the revalorization of AS.

5.
Int J Biol Macromol ; 223(Pt A): 684-701, 2022 Dec 31.
Article En | MEDLINE | ID: mdl-36356880

The efficacy of polylactic acid (PLA)/Magnesium (Mg)-based materials for driving stem cells toward bone tissue engineering applications requires specific Mg surface properties to modulate the interface of stem cells with the film. Here, we have developed novel PLA/Mg-based composites and explored their osteogenic differentiation potential on human adipose stem cells (hASCs). Mg-particles/polymer interface was improved by two treatments: heating in oxidative atmosphere (TT) and surface modification with a compatibilizer (PEI). Different contents of Mg particles were dispersed in PLA and composite surface and bulk properties, protein adsorption, stem cell-PLA/Mg interactions, osteogenic markers expressions, and lipids composition profile were evaluated. Mg particles were uniformly distributed on the surface and in the bulk PLA polymer. Improved and modulated particle-polymer adhesion was observed in Mg particle-treated composites. After 21 days in canonical growth culture conditions, hASCs on PLA/MgTT displayed the highest expression of the general osteogenic markers, RUNX2, SSP1, and BGLAP genes, Alkaline Phosphatase, type I Collagen, Osteopontin, and Calcium deposits. Moreover, by LC/MS QTOF mass-spectrophotometry lipidomic analysis, we found in PLA/MgTT-cells, for the first time, a remodeling of the lipid classes composition associated with the osteogenic differentiation. We ascribed these results to MgTT characteristics, which improve Mg availability and composite osteoinductive performance.


Magnesium , Osteogenesis , Humans , Magnesium/pharmacology , Cells, Cultured , Cell Proliferation , Polyesters/pharmacology , Cell Differentiation , Stem Cells , Polymers , Antigens, Differentiation , Adipose Tissue
6.
Polymers (Basel) ; 13(12)2021 Jun 14.
Article En | MEDLINE | ID: mdl-34198703

In the present work, anthocyanin (ACN) hybrid nanopigments were synthetized by using a natural pomegranate dye (PD) and calcined hydrotalcite (HT) and montmorillonite (MMT) nanoclays. A wide colour gamut was obtained with MMT-based nanopigments ranging from reddish to bluish hues caused by structural transformations of ACNs at different pH values. However, a buffer effect was observed with HT obtaining samples a similar final colour regardless of the synthesis conditions. Nanopigments added with a biomordant extracted from pomegranate peels showed a different colour compared to the incorporation of a commercial mordant due to the intrinsic colouring properties of the pomegranate bioadditive. The developed nanopigments were incorporated at 7 wt% loading to produce novel polyester-based bionanocomposites which were characterized in terms of thermal, mechanical and colour properties. The encapsulation of PD into the nanoclays improved its thermal stability, in particular for MMT-based nanopigments. The pH changes observed during the nanofillers synthesis affected the final colour of the MMT-based nanocomposites, inducing a general increase in ∆E* and a decrease in gloss values. Slight improvements were obtained in terms of elastic modulus for MMT-based polymer samples confirming the applicability of the developed bionanocomposites as colouring and reinforcement materials. A very similar environmental profile was obtained for MMT and HT-based nanofillers showing MMT-based nanopigments a slightly better general behaviour. The results of the LCA study evidenced the suitability of the processes used in this work to the circular bioeconomy approach through sustainable food waste management and the production of bioplastics using waste substrates.

7.
Polymers (Basel) ; 13(2)2021 Jan 16.
Article En | MEDLINE | ID: mdl-33467159

This study was dedicated to the functional characterization of innovative poly(lactic acid) (PLA)-based bilayer films containing lignocellulosic nanostructures (cellulose nanocrystals (CNCs) or lignin nanoparticles (LNPs)) and umbelliferone (UMB) as active ingredients (AIs), prepared to be used as active food packaging. Materials proved to have active properties associated with the antioxidant action of UMB and LNPs, as the combination of both ingredients in the bilayer formulations produced a positive synergic effect inducing the highest antioxidant capacity. The results of overall migration for the PLA bilayer systems combining CNCs or LNPs and UMB revealed that none of these samples exceeded the overall migration limit required by the current normative for food packaging materials in both non-polar and polar simulants. Finally, all the hydrophobic monolayer and bilayer films were completely disintegrated in composting conditions in less than 18 days of incubation, providing a good insight on the potential use of these materials for application as active and compostable food packaging.

8.
Polymers (Basel) ; 13(1)2020 Dec 28.
Article En | MEDLINE | ID: mdl-33379171

Biopo-lybutylene succinate (bioPBS) is gaining attention in the biodegradable polymer market due to its promising properties, such as high biodegradability and processing versatility, representing a potential sustainable replacement for fossil-based commodities. However, there is still a need to enhance its properties for certain applications, with aesthetical and mechanical properties being a challenge. The aim of the present work is to improve these properties by adding selected additives that will confer bioPBS with comparable properties to that of current counterparts such as polypropylene (PP) for specific applications in the automotive and household appliances sectors. A total of thirteen materials have been studied and compared, being twelve biocomposites containing combinations of three different additives: a commercial red colorant, itaconic acid (IA) to enhance color fixation and zirconia (ZrO2) nanoparticles to maintain at least native PBS mechanical properties. The results show that the combination of IA and the coloring agent tends to slightly yellowish the blend due to the absorbance spectra of IA and also to modify the gloss due to the formation of IA nanocrystals that affects light scattering. In addition, for low amounts of IA (4 wt %), Young's Modulus seems to be kept while elongation at break is even raised. Unexpectedly, a strong aging affect was found after four weeks. IA increases the hydrophilic behavior of the samples and thus seems to accelerate the hydrolization of the matrix, which is accompanied by an accused disaggregation of phases and an overall softening and rigidization effect. The addition of low amounts of ZrO2 (2 wt %) seems to provide the desired effect for hardening the surface while almost not affecting the other properties; however, higher amounts tends to form aggregates saturating the compounds. As a conclusion, IA might be a good candidate for color fixing in biobased polymers.

9.
Materials (Basel) ; 13(21)2020 Oct 31.
Article En | MEDLINE | ID: mdl-33142698

In the last decade, continuous research advances have been observed in the field of environmentally friendly polymers and polymer composites due to the dependence of polymers on fossil fuels and the sustainability issues related to plastic wastes. This research activity has become much more intense in the food packaging industry due to the high volume of waste it generates. Biopolymers are nowadays considered as among the most promising materials to solve these environmental problems. However, they still show inferior performance regarding both processability and end-use application. Blending currently represents a very cost-effective strategy to increase the ductility and impact resistance of biopolymers. Furthermore, different lignocellulosic materials are being explored to be used as reinforcing fillers in polymer matrices for improving the overall properties, lower the environmental impact, and also reduce cost. Moreover, the use of vegetable oils, waste derived liquids, and essential oils opens up novel opportunities as natural plasticizers, reactive compatibilizers or even active additives for the development of new polymer formulations with enhanced performance and improved sustainability profile.

10.
Nanomaterials (Basel) ; 10(11)2020 Oct 31.
Article En | MEDLINE | ID: mdl-33142867

Herein we present the production of novel nanocomposite films consisting of polylactic acid (PLA) polymer and the inclusion of nanoparticles of lignin (LNP), ZnO and hybrid ZnO@LNP (ZnO, 3.5% wt, ICP), characterized by similar regular shapes and different diameter distribution (30-70 nm and 100-150 nm, respectively). The obtained set of binary, ternary and quaternary systems were similar in surface wettability and morphology but different in the tensile performance: while the presence of LNP and ZnO in PLA caused a reduction of elastic modulus, stress and deformation at break, the inclusion of ZnO@LNP increased the stiffness and tensile strength (σb = 65.9 MPa and EYoung = 3030 MPa) with respect to neat PLA (σb = 37.4 MPa and EYoung = 2280 MPa). Neat and nanocomposite PLA-derived films were suitable for adult human bone marrow-mesenchymal stem cells and adipose stem cell cultures, as showed by their viability and behavior comparable to control conditions. Both stem cell types adhered to the films' surface by vinculin focal adhesion spots and responded to the films' mechanical properties by orchestrating the F-actin-filamin A interaction. Collectively, our results support the biomedical application of neat- and nanocomposite-PLA films and, based on the absence of toxicity in seeded stem cells, provide a proof of principle of their safety for food packaging purposes.

11.
Polymers (Basel) ; 12(10)2020 Sep 29.
Article En | MEDLINE | ID: mdl-33003627

In the present work, the effect of different bran content on the overall thermomechanical behavior of plasticized wheat flours (thermoplastic wheat flour; TPWF) was investigated. Refined flour (F0) with negligible bran fiber content, F1 flour (whole grain flour, 20% wt. bran), F3 (50% wt. bran) and F2 (F1:F3, 50:50) film samples were realized by extrusion process. The effect of TPWF blending with two different biopolymers (polycaprolactone and poly butyrate adipate terephthalate), combined with the presence of citric acid as compatibilizer was also considered. Results from FESEM analysis and tensile characterization demonstrated that PCL was able to reach improved compatibility with the plasticized flour fraction at intermediate bran content (F2 based formulation) when 25% wt. of biopolymeric phase was added. Additionally, it was proved that improvements can be achieved in both thermal and mechanical performance when higher shear rate (120 rpm) and low temperature profiles (Tset2 = 130-135-140 °C) are selected. Disintegrability of the TPWF basic formulations in compositing conditions within 21 days was also confirmed; at the same time, an absence of any phytotoxic event of compost itself was registered. The obtained results confirmed the suitability of these materials, realized by adding different bran contents, to mechanically compete with bioplastics obtained by using purified starches.

12.
Polymers (Basel) ; 12(11)2020 Oct 28.
Article En | MEDLINE | ID: mdl-33126539

Natural dyes obtained from agro-food waste can be considered promising substitutes of synthetic dyes to be used in several applications. With this aim, in the present work, we studied the use of chlorophyll dye (CD) extracted from broccoli waste to obtain hybrid nanopigments based on calcined hydrotalcite (HT) and montmorillonite (MMT) nanoclays. The synthesized chlorophyll hybrid nanopigments (CDNPs), optimized by using statistical designed experiments, were melt-extruded with a polyester-based matrix (INZEA) at 7 wt% loading. Mechanical, thermal, structural, morphological and colour properties of the obtained bionanocomposites were evaluated. The obtained results evidenced that the maximum CD adsorption into HT was obtained when adding 5 wt% of surfactant (sodium dodecyl sulphate) without using any biomordant and coupling agent, while the optimal conditions for MMT were achieved without adding any of the studied modifiers. In both cases, an improvement in CD thermal stability was observed by its incorporation in the nanoclays, able to protect chlorophyll degradation. The addition of MMT to INZEA resulted in large ΔE* values compared to HT incorporation, showing bionanocomposite green/yellow tones as a consequence of the CDNPs addition. The results obtained by XRD and TEM revealed a partially intercalated/exfoliated structure for INZEA-based bionanocomposites, due to the presence of an inorganic filler in the formulation of the commercial product, which was also confirmed by TGA analysis. CDNPs showed a reinforcement effect due to the presence of the hybrid nanopigments and up to 26% improvement in Young's modulus compared to neat INZEA. Finally, the incorporation of CDNPs induced a decrease in thermal stability as well as limited effect in the melting/crystallization behaviour of the INZEA matrix. The obtained results showed the potential use of green natural dyes from broccoli wastes, adsorbed into nanoclays, for the development of naturally coloured bionanocomposites.

13.
Carbohydr Polym ; 246: 116631, 2020 Oct 15.
Article En | MEDLINE | ID: mdl-32747266

Fully biobased blends of thermoplastic starch and a poly(butylene cyclohexanedicarboxylate)-based random copolyester containing 25 % of adipic acid co-units (PBCEA) are prepared by melt blending and direct extrusion film casting. The obtained films are characterized from the physicochemical and mechanical point of view and their fragmentation under composting conditions is evaluated. The results demonstrate that the introduction of adipic acid co-units in the PBCE macromolecular chains permits to decrease the blending temperature, thus avoiding unwanted starch degradation reactions. Moreover, the presence of small amounts of citric acid as compatibilizer further improves the interfacial adhesion between the two components and promotes the formation of micro-porosities within the films. The synergistic combination of these factors leads to the development of materials showing an elastomeric behavior, i.e. no evident yield and elongation at break higher than 450 %, good moisture resistance and fast fragmentation in compost.

14.
Polymers (Basel) ; 12(7)2020 Jun 28.
Article En | MEDLINE | ID: mdl-32605286

In this work, polyester-based nanocomposites added with laminar nanoclays (calcined hydrotalcite, HT, and montmorillonite, MMT) loaded with lemon waste natural dye (LD) and essential oil (LEO) were prepared and characterized. The optimal conditions to synthetize the hybrid materials were obtained by using statistically designed experiments. The maximum LD adsorption with HT was found using 5 wt% of surfactant (sodium dodecyl sulfate), 5 wt% of mordant (aluminum potassium sulfate dodecahydrate) and 50% (v/v) ethanol. For MMT, 10 wt% of surfactant (cetylpyridinium bromide), 5 wt% of mordant, 1 wt% of (3-aminopropyl) triethoxysilane and 100% distilled water were used. LEO adsorption at 300 wt% was maximized with MMT, 10 wt% of surfactant and 50 °C following an evaporation/adsorption process. The obtained hybrid nanofillers were incorporated in a polyester-based matrix (INZEA) at different loadings (3, 5, and 7 wt%) and the obtained samples were characterized in terms of thermal stability, tensile behavior, and color properties. HT_LEM-based samples showed a bright yellow color compared to MMT_LEM ones. The presence of lemon hybrid pigments in INZEA-based systems produced a remarkable variation in CIELAB color space values, which was more visible with increasing the nanofillers ratio. A limited mechanical enhancement and reduced thermal stability was observed with the nanopigments addition, suggesting a limited extent of intercalation/exfoliation of MMT and HT in the polymer matrix. MMT_LEM pigments showed higher thermal stability than HT_LEM ones. A significant increase in Young's modulus of nanocomposites loaded with hybrid LEO was observed compared to the biopolymer matrix. The LEO inclusion into the nanoclays efficiently improved its thermal stability, especially for MMT.

15.
Biomacromolecules ; 21(8): 3254-3269, 2020 08 10.
Article En | MEDLINE | ID: mdl-32602702

Considering the current context of research aiming at proposing new bioplastics with low costs and properties similar to fossil-based commodities currently on the market, in the present work, a hybrid blend containing a prevalent amount of cheap inedible cereal flour (70 wt %) and poly(butylene succinate) (PBS) (30 wt %) has been prepared by a simple, eco-friendly, and low-cost processing methodology. In order to improve the interfacial tension and enhance the adhesion between the different phases at the solid state, with consequent improvement in microstructure uniformity and in material mechanical and adhesive performance, the PBS fraction in the blend was replaced with variable amounts (0-25 wt %) of PBS-based green copolymer, which exerted the function of a compatibilizer. The copolymer is characterized by an ad hoc chemical structure, containing six-carbon aliphatic rings, also present in the flour starch structure. The two synthetic polyesters obtained through two-stage melt polycondensation have been deeply characterized from the molecular, thermal, and mechanical points of view. Copolymerization deeply impacts the polymer final properties, the crystallizing ability, and stiffness of the PBS homopolymer being reduced. Also, the prepared ternary blends were deeply investigated in terms of microstructure, thermal, and mechanical properties. Lastly, both pure blend components and ternary blends were subjected to disintegration experiments under composting conditions. The results obtained proved how effective was the compatibilizer action of the copolymer, as evidenced by the investigation conducted on morphology and mechanical properties. Specifically, the mixtures with 15 and 20 wt % Co appeared to be characterized by the best mechanical performance, showing a progressive increase of deformation while preserving good values of elastic modulus and stress. The disintegration rate in compost was found to be higher for the lower amount of copolymer in the ternary blend. However, after 90 days of incubation, the blend richest in copolymer content lost 62% of weight.


Flour , Triticum , Butylene Glycols , Polymers
16.
Polymers (Basel) ; 12(4)2020 Apr 06.
Article En | MEDLINE | ID: mdl-32268549

Polyester-based biocomposites containing INZEA F2® biopolymer and almond shell powder (ASP) at 10 and 25 wt % contents with and without two different compatibilizers, maleinized linseed oil and Joncryl ADR 4400®, were prepared by melt blending in an extruder, followed by injection molding. The effect of fine (125-250 m) and coarse (500-1000 m) milling sizes of ASP was also evaluated. An improvement in elastic modulus was observed with the addition of< both fine and coarse ASP at 25 wt %. The addition of maleinized linseed oil and Joncryl ADR 4400 produced some compatibilizing effect at low filler contents while biocomposites with a higher amount of ASP still presented some gaps at the interface by field emission scanning electron microscopy. Some decrease in thermal stability was shown which was related to the relatively low thermal stability and disintegration of the lignocellulosic filler. The added modifiers provided some enhanced thermal resistance to the final biocomposites. Thermal analysis by differential scanning calorimetry and thermogravimetric analysis suggested the presence of two different polyesters in the polymer matrix, with one of them showing full disintegration after 28 and 90 days for biocomposites containing 25 and 10 wt %, respectively, under composting conditions. The developed biocomposites have been shown to be potential polyester-based matrices for use as compostable materials at high filler contents.

17.
Materials (Basel) ; 13(3)2020 Jan 28.
Article En | MEDLINE | ID: mdl-32012947

The use of maleinized (MLO) and epoxidized (ELO) linseed oils as potential biobased plasticizers for lignin/natural fiber composites formulations with improved toughness was evaluated. Arboform®, a lignin/natural fiber commercial composite, was used as a reference matrix for the formulations. The plasticizer content varied in the range 0-15 wt % and mechanical, thermal and morphological characterizations were used to assess the potential of these environmentally friendly modifiers. Results from impact tests show a general increase in the impact-absorbed energy for all the samples modified with bio-oils. The addition of 2.5 wt % of ELO to Arboform (5.4 kJ/m2) was able to double the quantity of absorbed energy (11.1 kJ/m2) and this value slightly decreased for samples containing 5 and 10 wt %. A similar result was obtained with the addition of MLO at 5 wt %, with an improvement of 118%. The results of tensile and flexural tests also show that ELO and MLO addition increased the tensile strength as the percentage of both oils increased, even if higher values were obtained with lower percentages of maleinized oil due to the possible presence of ester bonds formed between multiple maleic groups present in MLO and the hydroxyl groups of the matrix. Thermal characterization confirmed that the mobility of polymer chains was easier in the presence of ELO molecules. On the other hand, MLO presence delayed the crystallization event, predominantly acting as an anti-nucleating agent, interrupting the folding or packing process. Both chemically modified vegetable oils also efficiently improved the thermal stability of the neat matrix.

18.
Polymers (Basel) ; 12(2)2020 Jan 30.
Article En | MEDLINE | ID: mdl-32019157

Calcium terephthalate anhydrous salts (CATAS), synthetized by reaction of terephthalic acid with metal (Ca) oxide were incorporated at different weight contents (0-30 wt. %) in recycled Poly(ethylene terephthalate) (rPET) by melt processing. Their structure, morphology, thermal and mechanical properties (tensile and flexural behavior) were investigated. Results of tensile strength of the different formulations showed that when the CATAS content increased from 0.1 to 0.4 wt. %, tangible changes were observed (variation of tensile strength from 65.5 to 69.4 MPa, increasing value for E from 2887 up to 3131 MPa, respectively for neat rPET and rPET_0.4CATAS). A threshold weight amount (0.4 wt. %) of CATAS was also found, by formation at low loading, of a rigid amorphous fraction at the rPET/CATAS interface, due to the aromatic interactions (π-π conjugation) between the matrix and the filler. Above the threshold, a restriction of rPET/CATAS molecular chains mobility was detected, due to the formation of hybrid mechanical percolation networks. Additionally, enhanced thermal stability of CATAS filled rPET was registered at high content (Tmax shift from 426 to 441 °C, respectively, for rPET and rPET_30CATAS), essentially due to chemical compatibility between terephthalate salts and polymer molecules, rich in stable aromatic rings. The singularity of a cold crystallization event, identified at the same loading level, confirmed the presence of an equilibrium state between nucleation and blocking effect of amorphous phase, basically related to the characteristic common terephthalate structure of synthetized Ca-Metal Organic Framework and the rPET matrix.

19.
Molecules ; 26(1)2020 Dec 29.
Article En | MEDLINE | ID: mdl-33383931

Polylactic acid (PLA) films containing 1 wt % and 3 wt % of lignin nanoparticles (pristine (LNP), chemically modified with citric acid (caLNP) and acetylated (aLNP)) were prepared by extrusion and characterized in terms of their overall performance as food packaging materials. Morphological, mechanical, thermal, UV-Vis barrier, antioxidant and antibacterial properties were assayed; appropriate migration values in food simulants and disintegration in simulated composting conditions were also verified. The results obtained indicated that all lignin nanoparticles succeeded in conferring UV-blocking, antioxidant and antibacterial properties to the PLA films, especially at the higher filler loadings assayed. Chemical modification of the fillers partially reduced the UV protection and the antioxidant properties of the resulting composites, but it induced better nanoparticles dispersion, reduced aggregates size, enhanced ductility and improved aesthetic quality of the films through reduction of the characteristic dark color of lignin. Migration tests and disintegration assays of the nanocomposites in simulated composting conditions indicated that, irrespectively of their formulation, the multifunctional nanocomposite films prepared behaved similarly to neat PLA.


Biodegradable Plastics/chemistry , Food Packaging , Lignin/chemistry , Nanocomposites/chemistry , Polyesters/chemistry , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Antioxidants/chemistry , Antioxidants/pharmacology , Biodegradable Plastics/pharmacology , Biphenyl Compounds/chemistry , Biphenyl Compounds/pharmacology , Carbamates/chemistry , Carbamates/pharmacology , Citric Acid/chemistry , Citric Acid/pharmacology , Fullerenes/chemistry , Fullerenes/pharmacology , Lignin/pharmacology , Nanocomposites/ultrastructure , Nanoparticles/chemistry , Nanoparticles/ultrastructure , Niacinamide/analogs & derivatives , Niacinamide/chemistry , Niacinamide/pharmacology , Polyesters/pharmacology , Pyrazoles/chemistry , Pyrazoles/pharmacology , Sunscreening Agents/chemistry , Sunscreening Agents/pharmacology
20.
Polymers (Basel) ; 11(12)2019 Dec 14.
Article En | MEDLINE | ID: mdl-31847354

Poly(ether ether ketone) (PEEK)-based nanocomposites have been realized with incorporation (0-30 wt %) of anhydrous calcium terephthalate salts (CATAS), synthetized by reaction of terephtalic acid with the metal (Ca) oxide, by means of a melt processing. Their structure, morphology, thermal, and mechanical properties have been investigated. Scanning electron microscopy observations confirmed homogeneous dispersion of nanometer-sized fillers and a toughened fracture morphology even at the higher content, while thermal characterization confirmed an unvaried thermal stability and unmodified crystalline structure of the reference PEEK matrix. A negligible nucleating effect was evidenced, while a blocking effect of the amorphous phase fraction provide composites with increased stiffness, confirmed by enhanced values of G' and shifts of glass transition peak to higher temperatures, for restriction in chain mobility imposed by CATAS. The proposed solutions aimed to enlarge the application range of high performance costly PEEK-based composites, by using thermally stable nanofillers with limited costs and easily controllable synthesis phase.

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