Synthesis and Characterization of In-Situ-Prepared Nanocomposites Based on Poly(Propylene 2,5-Furan Dicarboxylate) and Aluminosilicate Clays.
ABSTRACT: Poly(propylene 2,5-furan dicarboxylate) (PPF), or poly(trimethylene 2,5-furan dicarboxylate) (PTF), is a biobased alipharomatic polyester that is expected to replace its fossil-based terephthalate (PPT) and naphthate (PPN) homologues. PPF possesses exceptional gas barrier properties, but its slow crystallization rate might affect its success in specific applications in the future. Therefore, a series of PPF based nanocomposites with the nanoclays Cloisite®-Na (MMT), Cloisite®-20A (MMT 20A), and halloysite nanotubes (HNT) were synthesized via the in situ transterification and polycondensation method. The effect of the nanoclays on the structure, thermal, and crystallization properties of PPF was studied with several methods including infrared spectroscopy (IR), Nuclear Resonance Spectroscopy (¹H-NMR), Wide Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC). The insertion of the nanofillers in the polymer matrix altered the crystallization rates, and TGA results showed good thermal stability, since no significant mass loss occurred up to 300 °C. Finally, the degradation mechanism was studied in depth with Pyrolysis-Gas Chromatography/Mass Spectroscopy, and it was found that β-scission is the dominant degradation mechanism.
Project description:A one pot-two step procedure for the synthesis of diethyl furan-2,5-dicarboxylate (DEFDC) starting from mucic acid without isolation of the intermediate furan dicarboxylic acid (FDCA) was studied. Then, the production of three different kinds of furan-based polyesters- polyethylene-2,5-furan dicarboxylate (PEF), polyhydropropyl-2,5-furan dicarboxylate(PHPF) and polydiglycerol-2,5-furandicarboxylate (PDGF)-was realized through a Co(Ac)₂·4H₂O catalyzed polytransesterification performed at 160 °C between DEFDC and a defined diol furan-based prepolymer or pure diglycerol. In parallel to polymerization process, an unattended regioselective 1-OH acylation of glycerol by direct microwave-heated FDCA diester transesterification led to the formation of a symmetric prepolymer ready for further polymerization and clearly identified by 2D NMR sequences. Furthermore, the synthesis of a more soluble and hydrophilic diglycerol-based furanic polyester was also achieved. The resulting biobased polymers were characterized by NMR, FT-IR spectroscopy, DSC, TGA and XRD. The morphologies of the resulted polymers were observed by FE-SEM and the purity of the material by EDX.
Project description:The photo-oxidative degradation processes of bio-based PA11 nanocomposites containing montmorillonite (MMT) and the organo-modified Cloisite®30B were investigated to discriminate the influence of organo-modified components on the polymer durability. Indeed, despite the extensive studies reported, there are still ambiguous points to be clarified from the chemical point of view. To this aim, UV-aged materials were analyzed by Size Exclusion Chromatography (SEC), Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS). This enabled determining changes in both chemical structure and Molar Masses (MMs) induced by light, heat and oxygen exposure. The addition of organo-modified nanoclays strongly affected the PA11 light durability, triggering the macromolecular chains scission due to the typical ?H, Norrish I and II mechanisms. However, the main contribution in boosting the photo-oxidative degradation is induced by iron impurities contained into the clays. Conversely, thermo-oxidation process performed at 215 °C was unambiguously affected by the presence of the organo-modifiers, whose presence determined an enhancement of crosslinking reactions.
Project description:Iron particles of sizes between 6 and 20 nm forming aggregates of 57 ± 17 nm were synthesized by chemical reduction of iron precursors on the surface of montmorillonite (MMT). This active MMT-Fe powder was then uniformly distributed in a linear low-density polyethylene (LLDPE) matrix by extrusion at atmospheric conditions, as confirmed by wide-angle X-ray scattering (WAXS), which also detected a partial exfoliation of the nanoclays. Thermogravimetric analysis (TGA) did not detect any significant modification of the degradation temperature between nanocomposites and active nanocomposites. 57Fe Mössbauer spectroscopy evidenced the formation of a majority of iron boride in MMT-Fe as well as in the active film containing it. The LLDPE.Fu15.MMT-Fe3.75 and LLDPE.Fu15.MMT-Fe6.25 films had oxygen-scavenging capacities of 0.031 ± 0.002 and 0.055 ± 0.009 g(O2)/g(Fe), respectively, while the neat powder had an adsorption capacity of 0.122 g(O2)/g(Fe). This result confirms that the fresh film samples were partially oxidized shortly after thermomechanical processing (60% of oxidized species according to Mössbauer spectroscopy). No significant difference in oxygen permeability was observed when MMT-Fe was added. This was related to the relatively small film surface used for measuring the permeability. The reaction-diffusion model proposed here was able to reproduce the observed data of O2 adsorption in an active nanocomposite, which validated the O2 adsorption model previously developed for dried MMT-Fe powder.
Project description:In this study, cellulose acetate (CA) mixed-matrix membranes were fabricated through the wet-phase inversion method. Two types of montmorillonite (MMT) nanoclay were embedded separately: sodium montmorillonite (Na-MMT) and organo-montmorillonite (O-MMT). Na-MMT was converted to O-MMT through ion exchange reaction using cationic surfactant (dialkyldimethyl ammonium chloride, DDAC). Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) compared the chemical structure and composition of the membranes. Embedding either Na-MMT and O-MMT did not change the crystallinity of the CA membrane, indicating that the nanoclays were dispersed in the CA matrix. Furthermore, nanoclays improved the membrane hydrophilicity. Compared with CA<sub>Na-MMT</sub> membrane, CA<sub>O-MMT</sub> membrane had a higher separation efficiency and antifouling property. At the optimum concentration of O-MMT in the CA matrix, the pure water flux reaches up to 524.63 ± 48.96 L?m<sup>-2</sup>?h<sup>-1</sup>?bar<sup>-1</sup> with over 95% rejection for different oil-in-water emulsion (diesel, hexane, dodecane, and food-oil). Furthermore, the modified membrane delivered an excellent antifouling property.
Project description:Montmorillonite is a type of nanoclay that originates from the clay fraction of the soil and is incorporated into polymers to form nanocomposites with enhanced mechanical strength, barrier, and flammability properties used for food packaging, automotive, and medical devices. However, with implementation in such consumer applications, the interaction of montmorillonite-based composites or derived byproducts with biological systems needs to be investigated.Herein we examined the potential of Cloisite Na+ (pristine) and Cloisite 30B (organically modified montmorillonite nanoclay) and their thermally degraded byproducts' to induce toxicity in model human lung epithelial cells. The experimental set-up mimicked biological exposure in manufacturing and disposal areas and employed cellular treatments with occupationally relevant doses of nanoclays previously characterized using spectroscopical and microscopical approaches. For nanoclay-cellular interactions and for cellular analyses respectively, biosensorial-based analytical platforms were used, with induced cellular changes being confirmed via live cell counts, viability assays, and cell imaging.Our analysis of byproducts' chemical and physical properties revealed both structural and functional changes. Real-time high throughput analyses of exposed cellular systems confirmed that nanoclay induced significant toxic effects, with Cloisite 30B showing time-dependent decreases in live cell count and cellular viability relative to control and pristine nanoclay, respectively. Byproducts produced less toxic effects; all treatments caused alterations in the cell morphology upon exposure.Our morphological, behavioral, and viability cellular changes show that nanoclays have the potential to produce toxic effects when used both in manufacturing or disposal environments.The reported toxicological mechanisms prove the extensibility of a biosensorial-based platform for cellular behavior analysis upon treatment with a variety of nanomaterials.
Project description:This study examined the effect of nanoclays and surfactant on the hydrolytic degradation and biodegradation of poly(lactic acid) (PLA) and PLA nanocomposites. Organomodified montmorillonite (OMMT), unmodified montmorillonite (MMT) and an organomodifier (surfactant) for MMT (QAC) were extruded with PLA to produce PLA nanocomposites. The films were produced with the same initial molecular weight, thickness and crystallinity since these properties have a significant effect on the biodegradation process. The biodegradation experiments were carried out in an in-house built direct measurement respirometric system and were evaluated in inoculated vermiculite and vermiculite media for extended periods of time. Hydrolysis experiments were also conducted separately to decouple the abiotic/hydrolysis phase. The results showed no significant variation in the mineralization of PLA nanocomposites as compared to pristine PLA. The addition of nanoclays did not enhance the biodegradability of PLA when the initial parameters were strictly controlled. The hydrolysis test indicated that the nanoclays and surfactant did not aid in the degradation of PLA.
Project description:Addition of nanoclays into a polymer matrix leads to nanocomposites with enhanced properties to be used in plastics for food packaging applications. Because of the plastics' high stored energy value, such nanocomposites make good candidates for disposal via municipal solid waste plants. However, upon disposal, increased concerns related to nanocomposites' byproducts potential toxicity arise, especially considering that such byproducts could escape disposal filters to cause inhalation hazards. Herein, we investigated the effects that byproducts of a polymer polylactic acid-based nanocomposite containing a functionalized montmorillonite nanoclay (Cloisite 30B) could pose to human lung epithelial cells, used as a model for inhalation exposure. Analysis showed that the byproducts induced toxic responses, including reductions in cellular viability, changes in cellular morphology, and cytoskeletal alterations, however only at high doses of exposure. The degree of dispersion of nanoclays in the polymer matrix appeared to influence the material characteristics, degradation, and ultimately toxicity. With toxicity of the byproduct occurring at high doses, safety protocols should be considered, along with deleterious effects investigations to thus help aid in safer, yet still effective products and disposal strategies.
Project description:To regulate the crystallization of poly(trimethylene terephthalate) (PTT) retarded by melt blending with polycarbonate (PC), the crystallization of the PTT/PC blend was investigated employing nano-montmorillonite (MMT) as a crystallization promoter with PTT as the continuous phase. The results showed that MMT exhibits a significant promoting effect on PTT crystallization; the presence of 1 wt. % MMT shifts the initial and peak crystallization temperatures of the 70/30 PTT/PC blend to ~17 °C and ~32 °C, respectively. Additionally, the full width at half maximum (FWHM) narrows by ~45%, and the ?Hc increases by 3.7 J.g-1. The accelerating effect of MMT is determined by its distribution and dispersion which depends on the shear intensity, mixing mode, and loading. MMT is easier to exfoliate via the two-step method than by the one-step method. The distribution in the PTT phase is enriched along the phase interface forming an MMT layer. This endows sections of the PTT with abundant nuclei and thus crystallization is promoted markedly compared with the one-step method. Moreover, the finer MMT migrates more readily to the interface to cause a much smoother phase interface. However, a secondary crystallization peak appears when the shear force is not sufficient enough to make MMT finely dispersed, in case of the two-step method and the MMT content is increased to 3 wt. %. The mixing temperature shows little effect on the acceleration of MMT on the crystallization of PTT/PC compared with the shear force. Only when MMT did not exfoliate or uncomplete did the presence of epoxy resin help to promote crystallization because of the improved MMT dispersion.
Project description:Bio-based polyesters derived from 2,5-furandicarboxylic acid (FDCA), including poly (ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), and poly(butylene 2,5-furandicarboxylate) (PBF) have been synthesized and modified with 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO). Copolyesters with increased glass transition temperature, good barrier and better mechanical properties, as well as higher transparency were reported in this work. The chemical structures, composition, and sequence distribution of the copolyesters were determined by ¹H NMR and 13C NMR. The degree of random (R) was close to 1 for all the copolyesters, indicating their random chemical structures. With the introduction of 10% CBDO units, the semi-crystalline PEF and PPF were changed into completely amorphous polyesters and the higher transparency was easily achieved. The glass transition temperature was increased from 87 °C for PEF to 91.1 °C for PETF-18, from 55.5 °C for PPF to 63.5 °C for PPTF-18, and from 39.0 °C for PBF to 43.5 °C for PBTF-18. The barrier properties investigation demonstrated that although the O₂ and CO₂ barrier of PEF/PPF/PBF were decreased by the addition of CBDO units, the modified copolyesters still showed good barrier properties.
Project description:Bioinspired design has been central in the development of hierarchical nanocomposites. Particularly, the nacre-mimetic brick-and-mortar structure has shown excellent mechanical properties, as well as gas-barrier properties and optical transparency. Along with these intrinsic properties, the layered structure has also been utilized in sensing devices. Here we extend the multifunctionality of nacre-mimetics by designing an optically transparent and electron conductive coating based on PEDOT:PSS and nanoclays Laponite RD and Cloisite Na+. We carry out extensive characterization of the nanocomposite using transmittance spectra (transparency), conductive atomic force microscopy (conductivity), contact-resonance force microscopy (mechanical properties), and SEM combined with a variety of stress-strain AFM experiments and AFM numerical simulations (internal structure). We further study the nanoclay's response to the application of pressure with multifrequency AFM and conductive AFM, whereby increases and decreases in conductivity can occur for the Laponite RD composites. We offer a possible mechanism to explain the changes in conductivity by modeling the coating as a 1-dimensional multibarrier potential for electron transport, and show that conductivity can change when the separation between the barriers changes under the application of pressure, and that the direction of the change depends on the energy of the electrons. We did not observe changes in conductivity under the application of pressure with AFM for the Cloisite Na+ nanocomposite, which has a large platelet size compared with the AFM probe diameter. No pressure-induced changes in conductivity were observed in the clay-free polymer either.