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

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

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

Physical structure of P(VDF-TrFE)/barium titanate submicron composites

Dynamic Dielectric Spectroscopy and Thermo Stimulated Current were used to investigate of the dielectric relaxation of hybrid Poly(vinylidene-fluoride-trifluoroethylene)/barium titanate 700 nm composites with 0–3 connectivity. The results obtained by this method allow us to describe the physical structure of these composites in the glassy state at a nanometric scale. The decrease of the activation enthalpies and activation entropies involved in the dynamics of the α relaxation is attributed to: the decrease of Cooperative Rearranging Region sizes and an increase of intra/inter macromolecular interactions in the amorphous phase with the volume fraction

Dynamic mechanical behaviour of polyamide 11/Barium titanate ferroelectric composites

Dynamic mechanical analysis and tensile test have been used to characterize the mechanical behaviour of hybrid composites. Barium titanate (BaTiO3) is the submicron filler and polyamide 11 (PA 11) the matrix. The influence of volume fraction and particles size (ranging from 100 nm to 700 nm) of the inorganic phase on the composites mechanical properties have been checked. BaTiO3 dispersion in the matrix increases the tensile modulus of the composites and an evolution from ductile to fragile is observed for volume fractions above 12 vol%. The volume fraction dependence of the glassy shear modulus is well described by the Hashin and Shtrikman model indicative of an interaction lack between the organic and inorganic phases. The decrease of the glassy shear modulus with the filler size has been associated with the existence of softer organic/inorganic interfaces, in agreement with the previous hypothesis. The non linear variation of the rubbery modulus versus particles content is well described by the rubber elasticity model applied to a hydrogen bond network

Synthesis of novel room temperature chiral ionic liquids. application as reaction media for the heck arylation of aza-endocyclic acrylates.

New achiral and chiral RTILs were prepared using novel and/or optimized synthetic routes. These new series of imidazolinium, imidazolium, pyridinium and nicotine-derived ionic liquids were fully characterized including differential scanning calorimetry (DSC) analysis. The performance of these achiral and chiral room temperature ionic liquids (RTILs) was demonstrated by means of the Heck arylation of endocyclic acrylates employing arenediazonium salts and aryl iodides. The Heck arylations performed in the presence of these ionic entities, either as a solvent or as an additive, were effective leading to complete conversion of the substrate and good to excellent yield of the Heck adduct. In spite of the good performances, no asymmetric induction was observed in any of the cases studied. Two new diastereoisomeric NHC-palladium complexes were prepared in good yields from a chiral imidazolium salt and their structure characterized by X-ray diffraction. Overall, the Heck arylations employing arenediazonium tetrafluoroborates in RTILs were more effective than the traditional protocols employing aryl iodides in terms of reactivity and yields

Nanotexture influence of BaTiO3 particles on piezoelectric behaviour of PA 11/BaTiO3 nanocomposites

The piezoelectric activity of a hybrid ferroelectric nanocomposite, i.e. polyamide 11/barium titanate (BT), has been investigated for different loadings of BT particles. The BT volume fraction (/) was ranging from 0.024 to 0.4 with a particle size of 50, 100, 300 and 700 nm. The influence of polarization mode on the piezoelectric behaviour has been studied. The magnitude of the poling field used in this study is in the same order of magnitude of the one used for bulk BT i.e. significantly lower than for piezoelectric polymers. The optimum piezoelectric coefficient is reached when the amorphous phase of the polymeric matrix is in the liquid state i.e. for a polarization temperature higher than the glass transition and for time constant allowing macromolecular mobility. The composite piezoelectric activity decreases for particles size lower than 300 nm due to the loss of the tetragonal phase. The nanotexture of these particles has been investigated by transmission electron microscopy (TEM) and high-resolution TEM. A core shell structure has been observed. An increase of the longitudinal piezoelectric strain coefficient d33 with the raising of BT volume fraction was shown. Contrary to inorganic piezoelectric ceramics, the dielectric permittivity of hybrid composites remains moderate; therefore it allows the piezoelectric voltage coefficient of composites to be higher than ceramics

Dynamic mechanical properties of oral mucosa: comparison with polymeric soft denture liners.

The purpose of this work was to characterize the viscoelastic behaviour of oral mucosa and compare it with the dynamic mechanical properties of different soft liners. For this purpose, a sample of pig oral mucosa and six commercialized soft liner samples have been investigated. A comparison was also carried with the first suitable hard rubber for dental prosthetics: vulcanite. Creep recovery (CR) and dynamic mechanical analysis (DMA)have been used to determine the mechanical modulus of oral mucosa and soft liners respectively. The Poisson ratio is used to compare mucosa bulk modulus and soft liner shear modulus. The biomechanical concept of conventional complete dentures needs a good adjustment of dynamic mechanical impedance between the base and oral mucosa. The viscoelastic mechanical property of the oral mucosa as a referent biopolymer has been confirmed in vitro. The modulus value, adjusted for old patients in physiological conditions, is in the order of 3 MPa. This study underlines the plasticization effect of absorbed water on the mechanical properties of the underlying tissue. This study allows us to define some characteristics of the most adapted biomaterial according to the clinical exigency. The required biomaterial must display the following properties: compatibility and chemical resistance with biological environment perpetuated mechanical properties during physiological conditions and clinical use, good adjustment of dynamic mechanical impedance with supporting mucosa and easy sample processing

Changes in the physical structure and chain dynamics of elastin network in homocysteine-cultured arteries

The thermal and dielectric properties of the elastin network were investigated in arteries cultured with physiological and pathological concentrations of homocysteine, an aminoacid responsible of histological impairments in human arteries. The physical structure of this amorphous protein was investigated by differential scanning calorimetry (DSC). To explore the molecular dynamics of the elastin network in the nanometer range, we used thermally stimulated currents (TSC), a dielectric technique running at low frequency, and measuring the dipolar reorientations in proteins subjected to a static electrical field. Combining DSC and TSC experiments reveals the molecular mobility of the proteins, both in the glassy state and in the liquid state. Significant differences are evidenced in the physical structure and relaxation behavior of elastin network in cultured arteries (physiological and pathological concentrations of homocysteine) and discussed

Molecular mobility in piezoelectric hybrid nanocomposites with 0–3 connectivity: Volume fraction influence

ThermoStimulated Current and Dynamic Dielectric Spectroscopy studieswere carried out on hybrid ferroelectric Polyamide 11/Barium Titanate to investigate dielectric relaxationmodes. The correlated results obtained by both methods allow us to describe precisely the molecular mobility of this 0–3 nanocomposite; in this work we will focus on the influence of the 700 nm nanoparticles volume fraction. The dielectric spectroscopy shows that the molecularmobility associatedwith the liquid dynamic is not influenced by the volume fraction. The evolution of lowfrequency relaxation, observed by depolarization currents techniques, have been attributed to the decrease of Cooperative Rearranging Region size and the increase of intra/inter macromolecular interactions in the soft amorphous phase