Exploring the structural properties and enhancement of Opto-electrical investigations for the synthesized epoxy based polymers with local nanoscale structures

Epoxy networks of the diglycidyl ether of bisphenol A (DGEBA) were prepared using 4, 4′-diaminodiphenyl (44′DDS) and 3, 3′-diaminodiphenyl (33′DDS) sulfone diamines crosslinking hardeners. The structural, linear optical and mechanical properties of the investigated sample were analysed. Dynamic Mechanical Thermal Analysis and wide-angle x-ray diffraction were conducted to select a candidate presenting interesting thermo-mechanical properties and particular nanostructures embedded in an amorphous matrix. Our choice is therefore focused on DGEBA/33′DDS polymer for which, rocking curve measurements revealed the existence of two principal reflecting planes inclined to each other by about 0.27°. To highlight the potential effect of these interfaces, Thermally Stimulated Depolarization Current (TSDC) and Time Domain Spectroscopy measurements have been carried out. The application of the windowing polarization TSDC technique, in DGEBA/33′DDS polymer sample, gives an almost linear variation of the activation energies in the range between 3.65 and 4.09 eV. To our knowledge, this is the first study concerning epoxy polymers in which activation energies associated to ρ interfacial charge relaxations are calculated. To study the effect of the interfaces and trapped charge carriers, correlated by the angle x-ray diffraction measurements, the optical parameters were investigated. Our contribution will open a new avenue for developing the DGEBA/33′DDS polymer sustainable candidate in optoelectronic engineering applications

Surface acoustic wave sensors: From design to chemical and biological applications

International audienc

Caractérisation structurale et suivi du vieillissement par diffusion X aux petits angles d'un polymère époxyde (Contribution à l'étude des propriétés électriques)

Ce travail constitue une approche innovante mettant en complémentarité diverses techniques de caractérisation physicochimique, électrique et structurale. Menées sur un polymère époxyde, ces études ont pour principal objectif la compréhension des phénomènes et propriétés diélectriques associés aux charges d espace, ainsi que le suivi de leur évolution dans le temps ou suite à l application de contraintes extérieures. Les mesures de spectroscopie d impédance et de courant de dépolarisation thermo-stimulé (CDTS), ont mis en évidence des processus de relaxations dipolaires et interfaciales. L origine de ces phénomènes a pu être expliquée à partir des analyses physico-chimiques et structurales. Tout d abord à l aide des mesures de fluorescence X qui ont révélé la présence de deux types d impuretés, pouvant créer des états énergétiques plus ou moins profonds dans la bande interdite. Ensuite, par des mesures en réflectométrie X qui ont mis en évidence plusieurs structures ordonnées au sein d une matrice amorphe. Cette hétérogénéité structurale explique les mécanismes de piégeage et d accumulation des charges d espaces aux interfaces. De même, l ordre local favorisant la mobilité des charges, ces résultats donnent une première réponse quant à la valeur relativement élevée de la conductivité électrique du polymère, telle qu elle a pu être déterminée à partir des mesures des caractéristiques courant-tension. Des études de vieillissement accéléré ont également été menées. Les différents recuits appliqués ont contribué à la création de charges qui sont piégées dans des niveaux énergétiques de plus en plus profonds. Cela s est traduit par une diminution de la quantité de charges qui relaxent par activation thermique ainsi que par une diminution de la conductivité électrique des échantillons. Ces changements de propriétés électriques ont été corrélés aux changements structuraux qui se sont produits au sein du polymère, et dont la principale manifestation est la disparition progressive des structures ordonnées. Cette disparition de l ordre local a aussi été observée en l absence de contraintes thermiques (vieillissement naturel), où il a été montré que le comportement superficiel et en volume des échantillons n était pas identique.This work constitutes an innovative approach in epoxy based polymer characterization, where complementary physico-chemical, electric and structural techniques are used. The main objective of these studies is to understand both dielectric phenomena and properties associated to the space charges, as well as to follow-up their evolution in time or after the application of external constraints.Impedance spectroscopy and thermo-stimulated depolarization current (TSDC), measurements have highlighted dipolar and interfacial relaxations processes. Origin of these phenomena has been explained from physico-chemical and structural analyses. First, X-ray fluorescence measurements revealed the presence of two types of impurities, which are able to create deep energetic levels in the forbidden energy band. Then, X ray reflectometry measurements highlighted several periodic structures within an amorphous matrix. This structural heterogeneity explains the mechanisms of trapping and accumulation of space charges at the interfaces and gives a first reply as for the relatively high value of the polymer electric conductivity, calculated from current-voltage measurements.Accelerated ageing studies have been also carried out. They have shown that annealing creates charges which are trapped in increasingly deep energetic levels. Consequently, both the quantity of released charges and annealed samples conductivities have decreased.These electric properties changes have been correlated with the structural changes occurring within the polymer, and whose principal manifestation is the progressive disappearance of the ordered structures. This disappearance of the local periodicity has also been observed in the absence of thermal constraints (natural ageing), where it was shown that samples surface s behavior is different from the bulk.PARIS-CNAM (751032301) / SudocSudocFranceF

Tosylcellulose synthesis in aqueous medium

International audiencep-Toluenesulfonyl cellulose was prepared by reacting cellulose in aqueous medium, instead of via traditional routes, which involve the use of DMAc/LiCl, or more recently, ionic liquids. The influence of several parameters on the reaction efficiency has been studied; amount of tosylchloride, presence of triethylamine, reaction time and use of sodium hydroxide or sodium chloride. The resulting p-toluenesulfonyl cellulose samples were characterized by means of FTIR and NMR spectroscopy. The effects of solvent on the crystalline change during tosylation were investigated by X-ray diffraction (XRD). The degree of substitution (DS) was determined by 1H NMR and confirmed by X-ray photoelectron spectroscopy (XPS). Tosylcelluloses with DS from 0.1 to 1.7 have been prepared

Synthesis, structural and microstructural study of new FeNa0.5H1.5MoO5 hybrid material for highly efficient energy storage hybrid systems

International audienc

Chemical modification of kraft cellulose fibres: Influence of pretreatment on paper properties

International audienceChemical modifications of cellulose fibres (kraft pulp) in NaOH/H2O and NaCl/H2O systems were investigated. Handsheets were prepared that contained 25% of the modified fibres. Changes in the modified samples were examined by measuring their mechanical and optical properties and comparing them to those made with unmodified fibres. The observed differences were explained and supported by structural analyses, by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the NaOH/H2O pretreatment led to a significant deterioration of optical and strength properties of the handsheets. These modifications affected both the inner part of the crystalline cellulose (change from cellulose I to cellulose II) and the morphology of the fibers. Conversely, these properties slightly improved after propargylation, due to the propargyl functional groups. For the NaCl/H2O system, a significant enhancement of the mechanical properties of the handsheets was noted, such as an increase of up to 108% of the tear index. The propargylation further increased the tear index (by 157%). These enhancements were not accompanied by significant changes at both the micrometric and nanometric scales, except for the increase of the crystallinity index after propargylatio

Study of AC electrical conduction mechanisms in an epoxy polymer

International audienceThe AC conductivity of an epoxy resin was investigated in the frequency range 10−1−106 Hz at temperatures ranging from -100 to 120 °C. The frequency dependence of σac was described by the law: σac=ωε0ε′′HN+Aωs. The study of temperature variation of the exponent (s) reveals two conduction models: the AC conduction dependence upon temperature is governed by the small polaron tunneling mechanism (SPTM) at low temperature (-100 -60 °C) and the correlated barrier hopping (CHB) model at high temperature (80-120 °C)

Biological investigation using a shear horizontal surface acoustic wave sensor: Small "Click generated" DNA hybridization detection

International audienceWe have used a 104 MHz lithium tantalate (LiTaO3) surface acoustic wave (SAW) sensor to investigate DNA probes grafting and their further hybridization with natural and click generated (Cg-DNA) oligonucleotides. Natural DNA targets of different strand lengths, tosyl-di(tri, tetra) thymidine and azido-di(tri, tetra) thymidine oligonucleotides were tested. In our case, and besides the follow-up of a 34mer DNA hybridization, we detected complementarity between natural DNA probes and azido-tetra-thymidine for the first time, whereas previous hybridization studies reported a minimal of 10-mer oligonucleotides recognition length. We also demonstrated that contrarily to natural DNA, the synthesized oligonucleotides present stable bonds with complementary DNA strands. Frequency responses of both grafting and hybridization have shown the same shape: an exponential decay with different time constants, (187 ± 1) s and (68 ± 19) s for grafting and hybridization respectively. We have also shown that recognition between DNA strands and tetranucleotide analogues is comparable to natural 34mer DNA bases and presents the same time constant within uncertainties

Novel Approach for Modeling an Ionic Imprinted Polymer Based SAW Sensor with COMSOL Multiphysics

Modeling a Surface Acoustic Wave (SAW) sensor response as a chemosensor and not only as just an electronic transducer was performed with COMSOL Multiphysics. For this study, the SAW’s sensing area was functionalized with an ionic imprinted polymer (IIP), designed for the selective detection of lead ions. The idea consists in subdividing the IIP into elementary blocks whose physical properties can be modified separately. Three configurations have been envisaged: the IIP before and after lead ions extraction and the non-imprinted polymer (NIP). The generation of shear-horizontal waves on LiTaO3 piezoelectric substrate is confirmed by recording the displacement amplitude versus time, according to the three space directions. The sensors sensitivity is estimated from the delays induced by the incorporation of the lead ions in the IIP layer. To the best of our knowledge, this approach has never been presented in the literature

Chemical Modification of Kraft Cellulose Fibres: Influence of Pretreatment on Paper Properties

Chemical modifications of cellulose fibres (kraft pulp) in NaOH/H2O and NaCl/H2O systems were investigated. Handsheets were prepared that contained 25% of the modified fibres. Changes in the modified samples were examined by measuring their mechanical and optical properties and comparing them to those made with unmodified fibres. The observed differences were explained and supported by structural analyses, by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the NaOH/H2O pretreatment led to a significant deterioration of optical and strength properties of the handsheets. These modifications affected both the inner part of the crystalline cellulose (change from cellulose I to cellulose II) and the morphology of the fibers. Conversely, these properties slightly improved after propargylation, due to the propargyl functional groups. For the NaCl/H2O system, a significant enhancement of the mechanical properties of the handsheets was noted, such as an increase of up to 108% of the tear index. The propargylation further increased the tear index (by 157%). These enhancements were not accompanied by significant changes at both the micrometric and nanometric scales, except for the increase of the crystallinity index after propargylation