Controlling the Melt Resistance to Flow as a Possibility of Improving the Miscibility and the Time Behavior of Some Blends Based on Starch

The paper proves that the miscibility of some blends based on starch can be improved by finding for each of them the melt resistance to flow at which the nonstationary flow and the melt degradation are avoided and the developed shear rate homogenizes optimally the material composition. The obtained results show that, for process sensitive materials like starches, the border between good and less miscibility is so narrow that the window of melt processing conditions and the best formulation must be found for each of them. The improving of miscibility by controlling the melt resistance to flow proves to be a good method to prevent retrogradation and plasticizer leaching and so to handle the new compounds behavior during usage

New Evidences on the Process Sensitivity of Some Renewable Blends Based on Starch considering Their Melt Rheological Properties

The degradability and processability of new renewable materials based on starch and PVOH were studied using the melt flow index (MFI) method by measuring the melt rheological properties which depend not only on the extrusion conditions and material formulation but also on the macromolecule characteristics which can be modified by chemical degradation. These results were correlated with other material properties like color and cross-linking degree. The obtained results show that flowing in the melted state of the studied materials is accompanied by a second process of chains chemical degradation. It was observed that, at the same level of additivation, under identical extrusion conditions, the melted blends with corn starch as main component are highly mechanically sensitive and degrade mostly by chains scission and those with PVOH as major component are highly temperature sensitive and degrade mainly by cross-linking. The obtained results show also that each PVOH-starch blend requires particular formulation and individual windows of melt processing conditions. These results are a good proof that the MFI method is a good path to study the degradability and moldability of process sensitive polymeric materials like those based on starch and PVOH

Comparative Thermo-Mechanical Properties of Sustainable Epoxy Polymer Networks Derived from Linseed Oil

Considering its great industrial potential, epoxidized linseed oil (ELO) was crosslinked with different agents, both natural and synthetic: citric acid (CA, in the presence of water—W, or tetrahydrofuran—THF, as activator molecules) and Jeffamine D230, respectively, resulting bio-based polymeric matrices, studied further, comparatively, in terms of their properties, through different methods. Thermal curing parameters were established by means of Differential Scanning Calorimetry (DSC). Fourier transform Infrared Spectroscopy (FTIR) and DSC were used to identify the reactivity of each ELO-based formulation, discussing the influence of the employed curing systems under the conversion of the epoxy rings. Then, the obtained bio-based materials were characterized by different methods, establishing the structure–properties relation. Thermogravimetric analysis revealed higher thermal stability for the ELO_CA material when THF was used as an activator. Moreover, a higher glass transition temperature (Tg) with ~12 °C was registered for this material when compared with the one that resulted through the crosslinking of ELO with D230 conventional amine. Other important features, such as crosslink density, storage modulus, mechanical features, and water affinity, were discussed. Under the loop of a comprehensive approach, a set of remarkable properties were obtained for ELO_CA_THF material when compared with the one resulting from the crosslinking of ELO with the synthetic Jeffamine

Investigating the Synthesis and Characteristics of UV-Cured Bio-Based Epoxy Vegetable Oil-Lignin Composites Mediated by Structure-Directing Agents

Bio-based composites were developed from the epoxy derivatives of Lallemantia iberica oil and kraft lignin (ELALO and EpLnK), using UV radiation as a low energy consumption tool for the oxiranes reaction. To avoid the filler sedimentation or its inhomogeneous distribution in the oil matrix, different structure-directing agents (SDA) were employed: 1,3:2,4-dibenzylidene-D-sorbitol (DBS), 12-hydroxystearic acid (HSA) and sorbitan monostearate (Span 60). The SDA and EpLnK effect upon the ELALO-based formulations, their curing reaction and the performance of the resulting materials were investigated. Fourier-transform Infrared Spectrometry (FTIR) indicates different modes of molecular arrangement through H bonds for the initial ELALO-SDA or ELALO-SDA-EpLnK systems, also confirming the epoxy group’s reaction through the cationic mechanism for the final composites. Gel fraction measurements validate the significant conversion of the epoxides for those materials containing SDAs or 1% EpLnK; an increased EpLnK amount (5%), with or without SDA addition, conduced to an inefficient polymerization process, with the UV radiation being partially absorbed by the filler. Thermo-gravimetric and dynamic-mechanical analyses (TGA and DMA) revealed good properties for the ELALO-based materials. By loading 1% EpLnK, the thermal stability was improved to with 10 °C (for Td3%) and the addition of each SDA differently influenced the Tg values but also gave differences in the glassy and rubbery states when the storage moduli were interrogated, depending on their chemical structures. Water affinity and morphological studies were also carried out

Influence of Graphene Oxide Concentration when Fabricating an Electrochemical Biosensor for DNA Detection

We have investigated the influence exerted by the concentration of graphene oxide (GO) dispersion as a modifier for screen printed carbon electrodes (SPCEs) on the fabrication of an electrochemical biosensor to detect DNA hybridization. A new pretreatment protocol for SPCEs, involving two successive steps in order to achieve a reproducible deposition of GO, is also proposed. Aqueous GO dispersions of different concentrations (0.05, 0.1, 0.15, and 0.2 mg/mL) were first drop-cast on the SPCE substrates and then electrochemically reduced. The electrochemical properties of the modified electrodes were investigated after each modification step by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), while physicochemical characterization was performed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Finally, the sensing platform was obtained by the simple adsorption of the single-stranded DNA probe onto the electrochemically reduced GO (RGO)-modified SPCEs under optimized conditions. The hybridization was achieved by incubating the functionalized SPCEs with complementary DNA target and detected by measuring the change in the electrochemical response of [Fe(CN)6]3–/4– redox reporter in CV and EIS measurements induced by the release of the newly formed double-stranded DNA from the electrode surface. Our results showed that a higher GO concentration generated a more sensitive response towards DNA detection

Novel Nanocomposites Based on Functionalized Magnetic Nanoparticles and Polyacrylamide: Preparation and Complex Characterization

This paper reports the synthesis and complex characterization of nanocomposite hydrogels based on polyacrylamide and functionalized magnetite nanoparticles. Magnetic nanoparticles were functionalized with double bonds by 3-trimethoxysilyl propyl methacrylate. Nanocomposite hydrogels were prepared by radical polymerization of acrylamide monomer and double bond modified magnetite nanoparticles. XPS spectra for magnetite and modified magnetite were recorded to evaluate the covalent bonding of silane modifying agent. Swelling measurements in saline solution were performed to evaluate the behavior of these hydrogels having various compositions. Mechanical properties were evaluated by dynamic rheological analysis for elastic modulus and vibrating sample magnetometry was used to investigate the magnetic properties. Morphology, geometrical evaluation (size and shape) of nanostructural characteristics and the crystalline structure of the samples were investigated by SEM, HR-TEM and selected area electron diffraction (SAED). The nanocomposite hydrogels will be further tested for the soft tissue engineering field as repairing scaffolds, due to their mechanical and magnetization behavior that can stimulate tissue regeneration

Layered Clay–Graphene Oxide Nanohybrids for the Reinforcement and Fire-Retardant Properties of Polyurea Matrix

Nanostructures are more and more evolved through extensive research on their functionalities; thus, the aim of this study was to obtain layered clay–graphene oxide nanohybrids with application as reinforcing agents in polyurea nanocomposites with enhanced thermal–mechanical and fire-retardant properties. Montmorillonite (MMT) was combined with graphene oxide (GO) and amine functionalized graphene oxide (GOD) through a new cation exchange method; the complex nanostructures were analyzed through FTIR and XPS to assess ionic interactions between clay layers and GO sheets by C1s deconvolution and specific C sp3, respective/ly, C-O secondary peaks appearance. The thermal decomposition of nanohybrids showed a great influence of MMT layers in TGA, while the XRD patterns highlighted mutual MMT and GO sheets crystalline-structure disruption by the d (002) shift 2θ = 6.29° to lower values. Furthermore, the nanohybrids were embedded in the polyurea matrix, and the thermo-mechanical analysis gave information about the stiffness of MMT–GO nanocomposites, while GOD insertion within the MMT layers resulted in a 30 °C improvement in the Tg of hard domains, as shown in the DSC study. The micro CT analysis show good dispersion of inorganic structures within the polyurea, while the SEM fracture images revealed smooth surfaces. Cone calorimetry was used to evaluate fire-retardant properties through limiting the oxygen index, and MMT–GOD based nanocomposites showed a 35.4% value

Grafting versus Crosslinking of Silk Fibroin-g-PNIPAM via Tyrosine-NIPAM Bridges

This paper reports the synthesis and complex characterization of novel polymeric networks based on the crosslinking of Bombyx mori silk fibroin via poly(N-isopropylacrylamide) bridges generated by an ammonium cerium nitrate redox system. The research study gives an understanding of the polymerization mechanism in terms of the generation of radical sites, radical growth and termination reaction, as well as the involvement of modifications on silk fibroin structure and properties. The physico-chemical characterization was carried out by FTIR-ATR, X-ray photoelectron spectroscopy and RAMAN spectroscopy with unravelling the chemical modification. The structural characterization and spatial arrangement by secondary structure were carried out by X-ray diffraction and circular dichroism. The thermal behavior and thermal stability were evaluated by differential scanning calorimetry and thermogravimetric analysis. The novel complex polymer network is intended to be used in the field of smart drug delivery systems

Increasing the Efficiency of Multilayered Silicate Melt Incorporation into Starch-Based Polymeric Matrices

This article compares two exfoliation options of multilayered silicate, one considering the action of shear stress and temperature during melt compounding and another taking into account the action of the thermo-mechanical pretreatment of multilayered silicate in a plasticizer common to the starch and polyvinyl alcohol (PVOH), the two polymers from the compound. Increasing the action time of the shear stress and temperature during melt compounding proved to be an ineffective method for silicate exfoliation following the high degradability of starch and PVOH under thermo-mechanical conditions and the loss of hydration of the multilayered silicate under thermo-mechanical conditions. The obtained results prove that, by pretreating before embedding into the desired starch-PVOH matrix, it was possible to cancel the electrostatic attractions between the component lamellae of a multilayered silicate. During melt compounding with the two polymers, new attractions between the obtained lamellae and the polar groups of each polymer from the blend were settled, and so, without the usage of a liquid plasticizer, exfoliated intercalated nanocomposites were achieved. The improved properties and the practical importance of the new nanocomposites regards the obtaining of a non-degradable material that has a white color, better elastic properties and thermal stability, and a higher dissipation capacity of deformation energy

Control of Dielectric and Mechanical Properties of Styrenic Block Copolymer by Graphite Incorporation

The structure–property relationship of dielectric elastomers, as well as the methods of improving the control of this relationship, has been widely studied over the last few years, including in some of our previous works. In this paper, we study the control, improvement, and correlation, for a significant range of temperatures, of the mechanical and dielectric properties of polystyrene-b-(ethylene-co-butylene)-b-styrene (SEBS) and maleic-anhydride-grafted SEBS (SEBS-MA) by using graphite (G) as filler in various concentrations. The aim is to analyze the suitability of these composites for converting electrical energy into mechanical energy or vice versa. The dielectric spectroscopy analysis performed in the frequency range of 10 to 1 MHz and at temperatures between 27 and 77 °C emphasized an exponential increase in real permittivity with G concentration, a low level of dielectric losses (≈10−3), as well as the stability of dielectric losses with temperature for high G content. These results correlate well with the increase in mechanical stiffness with an increase in G content for both SEBS/G and SEBS-MA/G composites. The activation energies for the dielectric relaxation processes detected in SEBS/G and SEBS-MA/G composites were also determined and discussed in connection with the mechanical, thermal, and structural properties resulting from thermogravimetric analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses