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

Heating Effects on Structural and Electrical Properties of Polyetherimide

Abstract: Problem statement: Polyetherimide (PEI) has several uses such as electrical insulation. It can undergo different constraints like heat or high voltage which influence its performances as insulator. In this study, the effects of heating on structural and electrical properties of polyetherimide (Ultem 1000) are studied. Approach: PEI samples were heated at different temperatures below the glass transition temperature (175, 190 and 205°C). Different complementary techniques were used to investigate structural alterations and dielectric relaxations. These are infrared (IR) spectroscopy, Differential Scanning Calorimetry (DSC), Thermally Stimulated Depolarisation Current (TSDC) technique and Dielectric Spectroscopy (DS). Results: Physical ageing was revealed in heated samples by DSC analysis. DS and TSDC results have shown that dipolar relaxations are affected by heating. The amount of relaxing dipoles decreases when the material is heated at 190°C. Conclusion/Recommendations: The heating of polyetherimide at 190°C leads to a stabilisation of charges in deeper energetic levels which influences the insulating character of the material

Study of electrical properties of polymethylmethacrylate treated in aqueous and saline environments

Polymethylmethacrylate (PMMA) is one of the most studied polymers in the last years due to its outstanding mechanical and physical-chemical properties. This material is used in various applications in which it can be subjected to different constraints. In this work, PMMA samples were submitted to thermal treatment (at 100 °C for 20 min) in aqueous and saline environments. We studied the hydrothermal effect as well as the saline environment effect on electrical properties of PMMA by means of thermal step method (TSM) and thermally stimulated depolarization current (TSDC) technique. It was found that polarization was significantly influenced by the hydrothermal treatment realized particularly in a saline medium. α- and ρ-relaxations were observed in all TSDC spectra. For each treated sample, ρ-relaxation peak is more intensive than the dipolar one and the corresponding releasing charge quantity increases

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

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

Optical, Dielectric Properties and Energy Storage Efficiency of ZnO/Epoxy Nanocomposites

International audienceZnO/epoxy nanocomposites were prepared in five different contents (0.25–3.0 wt%). Optical, thermal and dielectric properties have been examined as a function of ZnO nanoparticles. The absorption optical spectra exhibit a broad intense peak assigned to the n–π* (HOMO–LUMO) transitions. Nanocomposite with 3.0 wt% ZnO sample completely blocks UV-light radiations in the region from 300 to 480 nm, which allowed that the prepared material to be used for UV-Shielding devices. The optical band gap is found to decrease with increasing filler ZnO concentrations. This might be due to increasing the density of defect states. Permittivity and electric modulus formalisms are used to analyze and interpret the experimental data. γ relaxation is observed in the low temperature region, which is attributed to the rearrangement of small parts of the polymeric chains. The α relaxation and the Maxwell–Wagner–Sillars (MWS) effect, attributed to the glass rubber transition of the polymeric matrix and the interfacial polarization phenomena respectively, are observed in the high temperature region. Using Havriliak–Negami approach, the temperature dependence of relaxation time for MWS and γ relaxations follows an Arrhenius behavior while the α relaxation time is well described by the Vogel–Fulcher–Tamann behavior. The activation energies of all relaxation modes were calculated and discussed. The energy density of the investigated samples is significantly enhanced. It is about 2 × 10−6 J/m3 for nanocomposite with 3.0 wt% ZnO at 20 °C.These results indicate that the effect of ZnO nanoparticles makes the proposed materials suitable candidates for energy storage applications

Exploring the optical and dielectric properties of bifunctional and trifunctional epoxy polymers

Two polymers were prepared from diglycidyl ether of bisphenol A (DGEBA) and triglycidyl p-aminophenol (TGAP) epoxy resins, using the same hardener diethylenetriamine (DETA). The obtained polymers were compared in terms of structural, optical, mechanical, thermal and dielectric properties. Dielectric spectroscopy and dynamic mechanical analysis indicated the presence of dipolar dielectric relaxations in both polymers, and interfacial one only for TGAP/DETA, which is consistent with XRD findings. Different approaches were considered to fit electrical modulus and conductivity and to estimate the relaxation times and activation energies according to temperature. For optical measures, a novel result processing approach is proposed for an accurate determination of the polymers bandgap and for highlighting the existence of additional energy transition level for TGAP. Results indicate that this polymer could be a potential candidate for use as a protective film and as UV/blue-light filter for screens and window

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)

A comparative study of structural and dielectric properties of diglycidyl ether of bisphenol A (DGEBA) cured with aromatic or aliphatic hardeners

International audienceThis study aims to present structural and dielectric comparisons between two epoxy polymers. These polymers are realized by curing diglycidyl ether of bisphenol A (DGEBA) resin with either aliphatic 1,3-diaminopropane (PDA) or aromatic 4,4′-diaminodiphenyl sulfone (DDS) hardeners. They are called DGEBA/PDA and DGEBA/DDS. Several complementary techniques have been used in the present study. The structural analysis was performed using grazing incidence X-ray reflectometry. It reveals the presence of a locally ordered nanostructure in the DGEBA/DDS polymer and an amorphous character for the DGEBA/PDA one. Dielectric characterization was carried by means of dielectric relaxation spectroscopy (DRS), thermally stimulated depolarization current (TSDC) and time domain spectroscopy (TDS). DRS measurements performed over wide ranges of temperature (−80 to 160 °C) and frequency (10−1–106 Hz) showed the presence of dipolar γ and α relaxations in both polymers. Nevertheless, the interfacial Maxwell–Wagner–Sillars (MWS) relaxation appeared only in DGEBA/DDS. This can be related to the local nanostructure within this polymer, which can give rise to interfaces. Relaxation parameters were deduced from the best fits of experimental data with the Havriliak–Negami model. The calculated fragility index indicates that DGEBA/DDS is more fragile than DGEBA/PDA. The loss factor ε′′(f) was calculated from the isothermal discharging current measurements, using Hamon approximation. Thanks to this ε′′ calculation an interfacial relaxation was revealed in the frequency range of 10−3–10−1 Hz for each investigated polymer

Effects of curing agent on conductivity, structural and dielectric properties of an epoxy polymer

International audienceTwo epoxy polymers were prepared by curing the diglycidyl ether of bisphenol A (DGEBA) epoxy resin with two hardeners: the ethylenediamine (EDA) and the 3,3′-diaminodiphenyl sulfone (33′DDS) which are respectively aliphatic and aromatic. Structural properties of DGEBA/EDA and DGEBA/33′DDS polymers were investigated by means of grazing incidence X-ray reflectometry. Their dielectric properties were studied using the dielectric relaxation spectroscopy (DRS) over wide ranges of temperature (from −80 to 200 °C) and frequency (from 10−1–106 Hz), and thermally stimulated depolarization current (TSDC) technique. X-ray data revealed the presence of a locally periodic nanostructure in polymer cured with the aromatic hardener (DGEBA/33′DDS). γ and α dipolar relaxations were highlighted for the two polymers while the Maxwell–Wagner–Sillars (MWS) relaxation appears only in the DGEBA/33′DDS. The electric modulus data were fitted using Havriliak–Negami approch. Conductive properties of epoxies were investigated. Ac conductivity data reveal that DGEBA/EDA is more conductive than the DGEBA/33′DDS