Hydrated elastin: Dynamics of water and protein followed by dielectric spectroscopies

The dielectric properties of elastin were investigated at different levels of hydration and specifically at the limit of freezable water apparition. The quantification of freezable water was performed by Differential Scanning Calorimetry (DSC). Two dielectric techniques were used to explore the dipolar relaxations of hydrated elastin: dynamic dielectric spectroscopy (DDS), performed isothermally with the frequency varying from 10(-2) to 3.10(-6) Hz, and the technique of thermally stimulated depolarization currents (TSDC), an isochronal spectrometry running at variable temperature, analogous to a low frequency spectroscopy {10(-3)– 10(-2) Hz}. A complex relaxation map was evidenced by the two techniques. Assignments for the different processes can be proposed by the combination of DDS and TSDC experiments and the determination of the activation parameters of the relaxation times. As already observed for globular proteins, the concept of "solvent-slaved" protein motions is checked for the fibrillar hydrated elastin

Molecular mobility interpretation of the dielectric relaxor behavior in fluorinated copolymers and terpolymers

Thermo Stimulated Current and Dynamic Dielectric Spectroscopy have been applied to investigate dielectric relaxation modes of poly(vinylidene-fluoride trifluoroethylene) copolymer and poly(vinylidene-fluoridetrifluoroethylene-chlorofluoroethylene) terpolymer. The aim of this work is to check the molecular origin of the ferroelectric relaxor behavior of the terpolymer. The combination of data obtained by both dielectricmethods allows us to describe themolecular mobility of the amorphous phase and the cooperativity of the order/disorder dipolar transition in the crystalline phase. The introduction of 1,1-chlorofluoroethylene units in the main chain induces an increase of the Cooperative Rearranging Region size associatedwith less ordered and smaller crystallites. This morphological evolution is responsible of a lack of cooperativity and it explains the dielectric relaxor behavior of the poly(vinylidene-fluoride-trifluoroethylene-chloroethylene) terpolymer

Influence of hydrogen bonds on glass transition and dielectric relaxations of cellulose

The molecular dynamics in hydrated cellulose has been investigated by a combination of thermal analyses and dielectric spectroscopy. Differential scanning calorimetry shows the dependence upon hydration of the glass transition temperature Tg. A physical ageing phenomenon has been observed. At the molecular scale, bound water is hydrogen bonded to polar sites of cellulose macromolecules. At the macroscopic scale, water molecules play the role of a plasticizer for cellulose lowering its Tg. Dynamic dielectric spectroscopy combined with thermostimulated currents have allowed us to follow more localized molecular mobility. The β relaxation mode is characterized by activation entropies that vanish for higher water contents indicating molecular mobility localization. It is plasticized by water like the glass transition. This analogy is explained by a common origin of both mechanisms: the mobility of the cellulose backbone. The evolution of the γ mode upon hydration follows an anti-compensation law. Water acts as an anti-plasticizer in a hydrogen bonded network

Mechanical improvement of P(VDF-TrFE)/nickel nanowires conductive nanocomposites: Influence of particles aspect ratio

Nickel nanowires with high aspect ratio (250) were elaborated and incorporated into poly(vinylidene difluoride-trifluoroethylene) up to 30 vol% via solvent mixing way. These nanocomposites are characterized by a conductive behavior with a high electrical conductivity value (102 S m−1) above a very low percolation threshold (0.75 vol% of metallic nanowires). The introduction of nanowires strongly depressed the matrix crystallinity. Static and dynamic mechanical analysis have been realized at low nanowire volume fraction (< 10 vol%). Below 5 vol% of nanowires, nanocomposites remain ductile. The dynamic mechanical properties are related to the volume fraction of nanowires. A strong increase of the viscoelastic contribution related to the increase of the percentage of amorphous phase is observed. The major effect is the increase of the rubbery modulus. The highest increase of 300% is obtained for only 5 vol% of nanowires; it represents an original mechanical result for low filled composites. The dependence versus nanowire content has been described by adapting the Halpin–Tsai model to high aspect ratio filler. Metallic nanowires create additional entanglements that are randomly distributed in the rubbery polymeric matrix. With their low percolation threshold, metallic nanowires based nanocomposites constitute a new class of multifunctional materials with a high conductivity associated with a ductile polymer matrix characterized by a high rubbery modulus

Electrical conductivity improvement of aeronautical carbon fiber reinforced polyepoxy composites by insertion of carbon nanotubes

An increase and homogenization of electrical conductivity is essential in epoxy carbon fiber laminar aeronautical composites. Dynamic conductivity measurements have shown a very poor transversal conductivity. Double wall carbon nanotubes have been introduced into the epoxy matrix to increase the electrical conductivity. The conductivity and the degree of dispersion of carbon nanotubes in epoxy matrix were evaluated. The epoxy matrix was filled with 0.4 wt.% of CNTs to establish the percolation threshold. A very low value of carbon nanotubes is crucial to maintain the mechanical properties and avoid an overload of the composite weight. The final carbon fiber aeronautical composite realized with the carbon nanotubes epoxy filled was studied. The conductivity measurements have shown a large increase of the transversal electrical conductivity. The percolative network has been established and scanning electron microscopy images confirm the presence of the carbon nanotube conductive pathway in the carbon fiber ply. The transversal bulk conductivity has been homogenized and improved to 10−1 S·m−1 for a carbon nanotubes loading near 0.12 wt.%

Low filled conductive P(VDF-TrFE) composites: Influence of silver particles aspect ratio on percolation threshold from spheres to nanowires

Polymer composites filled with silver nanowires enable the highest value of electrical conductivity known up to now in the case of conductive nanoparticle dispersion with a percolation threshold less than 1 vol%. Silver nanowires with high aspect ratio were elaborated by two types of synthesis: electrochemical deposition in a template and polyol synthesis. For the first time the influence of each kind of nanowires in composites was studied and compared to spherical nanoparticles as reference. The value of percolation threshold and conductivity level above the percolation threshold were measured and compared. These silver nanowires were introduced into poly(vinylidenedifluoride-trifluoroethylene) in comparison to spherical silver nanoparticles. The preparation method modified the effective aspect ratio of nanowires. The low percolation threshold and the microscopy observations confirmed the good dispersion of nanowires in composites. The lowest percolation threshold was determined in the case of the polyol synthesis nanowires (0.63 vol%) in comparison with electrochemical deposited nanowires (2.2 vol%). The level of conductivity above the percolation threshold obtained with each kind of particles is in the same range near 100 S.m− 1. The value of electrical conductivity obtained above the percolation threshold is unusual at this low content of conductive filler and is observed for the first time in a conductive polymer composite

Molecular mobility in piezoelectric hybrid nanocomposites with 0-3 connectivity: Particles size influence

Polyamide 11/barium titanate nanocomposites have been studied by a combination of dynamic dielectric spectroscopy, thermo stimulated current and differential scanning calorimetry. The correlation between results obtained by dielectric and calorimetric methods allows us to describe the evolution of the physical structure of the hybrid nanocomposites. The molecular mobility of 0-3 connectivity nanocomposites has been explored. The influence of the nanoparticles size is specifically studied. The smaller sized fillers produce a shift of the relaxation modes observed above the glass transition temperature of polyamide 11 towards lower frequency. The increase of the organic/inorganic interface induces an increase of the ratio rigid amorphous phase/soft amorphous phase. The interfaces favour local ordering stabilized by hydrogen bonds at a nanometric scale

Analysis of gene mutation in plant cell wall by dielectric relaxation

Arabidopsis Thaliana is a plant composed mainly of cellulose and lignin. Geneticists need techniques able to make differences at the molecular level between modified plants (DML6, CAD C/D) and non-modified ones. Thermo-stimulated current (TSC) analysis is a promising route to identify gene mutations. For the non-modified plant, at low temperatures, TSC thermograms highlight three dielectric relaxation modes. From −150 to −110 ◦C, γCellulose is attributed to CH2OH and –OH groups of cellulose. Between −110 and −80 ◦C, βLignin is detected. From −80 to −40 ◦C, βCellulose is characteristic of the molecular mobility of glycosidic linkages. For the CAD C/D modified plants, only γCellulose and βLignin are observed; due to analogous enthalpy values, those modes have the same molecular origin as in the non-modified plant. So, the βLignin mode is associated with the molecular mobility of the lignin-OH groups. The CAD C/D gene mutation changes the chemical structure of lignin, which promotes hydrogen bonds in the network and inhibits molecular mobility of glucosidic rings. It is also interesting to note that the DML6 gene mutation induces a higher cooperativity of this βCellulose relaxation than in wild vegetal composites. In fact, this mutation promotes molecular mobility of glycosidic rings thanks to β1–4 glycosidic linkages

Study of dielectric relaxations in cellulose by combined DDS and TSC

In this work, thermally stimulated currents (TSC) analyses combined with dynamic dielectric spectroscopy (DDS) have been applied to the investigation of molecular mobility of cellulose. The correlation between results obtained by both methods allows us to attribute the low temperature DDS relaxation mode to the c-mode resolved in TSC. The values of its activation parameters point out that the chain mobility remains localized. At high temperature, the various dielectric relaxation phenomena are separated by applying a recent analytical protocol. The comparison between the activation enthalpy values obtained by DDS and TSC leads to the assignment of the socalled a-mode to cooperative movements of polymeric sequences. The Arrhenius behavior of a-relaxation time is explained using the strong/fragile pattern. The influence of water content on secondary and primary relaxation modes was examined as well

Electroactive influence of ferroelectric nanofillers on polyamide 11 matrix properties

Barium titanate ceramic powders have been incorporated in polyamide 11 to form homogeneous dispersion of particles in the matrix. Barium titanate/polyamide 11 nanocomposites have been synthesized using a solvent casting method with ultrasonic stirring to homogeneously disperse inclusions in the matrix. Composites with volume fraction of barium titanate / ranging from 0.01 to 0.4 were elaborated. Films were fabricated using a hot press method. Only the inclusions were poled in the matrix to form a ferroelectric particles/ unpoled matrix composite. Interactions between the particles and the matrix, pyroelectric and piezoelectric response were studied as a function of / by dynamic dielectric spectroscopy. Composites show interesting pyro-piezoelectric activity. Pyroelectric merit factor increases linearly and it reaches a limit value of 0.3 for a volume fraction / = 0.1