Polymer-polymer interaction, in the presence of a solvent as measured by viscometry

Dilute solution viscometry experiments have been carried out in five ternary polymer systems solvent(1)/polymer(2)/polymer(3). Values of the specific viscosity of polymer (3) in a ‘binary solvent’ formed by polymer(2) + solvent(1) have been used to determine the compatibility of the polymer blends. Krigbaum and Wall formalism has been used to predict compatibility which relies on an interaction parameter that depends on the concentration, weight fraction and molar mass of each polymer. To reduce the dependences and to clarify the criterion of compatibility, a parameter independent of polymer (3) composition and molar mass has been deduced. This parameter shows the same behaviour with polyme…

Modelling the Influence of Nanoparticles in the Phase Behaviour of an Epoxy/Polystyrene Mixture, 2

The influences of nanoparticle size and concentration on the thermodynamic behaviour of epoxy/polystyrene blends are evaluated in the framework of Ginzburg's simple analytical theory. Two approaches have been employed: NPEPO (for particles coated with epoxy groups) and NPFEN (for particles coated with phenyl groups). Using NPEPO, the particles are found to prefer the phase richer in epoxy, whereas the opposite occurs for NPFEN. The particles size significantly influences blend compatibility. When the particle radius Rp is about the same size as the radius of gyration R g of PS, the compatibility of blends increases with particle concentration, whereas for R p > R g , higher particle concent…

Curing of an epoxy resin modified with nanoclay monitored by dielectric spectroscopy and rheological measurements

Dielectric and rheological measurements have been performed in “real-time” to follow curing reaction on blends of a diglycidyl ether of bisphenol-A epoxy resin with 4,4-methylene bis(2,6-diethylaniline) hardener and different amounts of organically modified nanoclay (Nanofil 919) as modifier. The effect of the modifier and its amount on the curing reaction, as well as that of the curing temperature has been studied. Changes in molecular mobility in the reaction mixture have been investigated by dielectric relaxation spectroscopy. Evolutions of ionic conductivity and main relaxation have been analyzed and vitrification times have been obtained and compared with those obtained by rheological …

Renewable polyol obtained by microwave-assisted alcoholysis of epoxidized soybean oil: Preparation, thermal properties and relaxation process

[EN] The soybean oil polyol (SOP) use as feedstock in the polyurethane industry has been recently emphasized due to its excellent resistance to hydrolysis, which is also applicable in coatings and thermal insulation. In this article, the SOP was obtained by a very fast microwave-assisted alcoholysis of epoxidized soybean oil (ESO). The preparation method, thermal properties, and relaxation process were evaluated. High yields as opening and consumption epoxy group and selectivity of 99.8 mol%, 985 mol%, and 71.2 mol% were obtained. Through titrations, nuclear magnetic resonance and gel permeation chromatography were identified parameters as 0.32 mg KOH.g(-1) acid number, 190 mg KOH.g(-1) hyd…

Transparent thermoplastic polyurethanes based on aliphatic diisocyanates and polycarbonate diol

Segmented thermoplastic polyurethanes (PUs) were synthetized using polycarbonate diol as soft segment with a molar mass of 500 and as a hard segment 1,5-pentanediol with a combination of isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, differential mechanical analysis, Fourier transform infrared-attenuated total reflection spectroscopy, haze, transmittance, hardness, tensile properties and retention of tensile properties tests were employed to characterize the different PUs. The results of this study show that IPDI/HDI relation has a significant impact on the phase mixing, crystallinity and therefore on the PU’s properties. The variati…

Development of self-assembled bacterial cellulose–starch nanocomposites

Abstract A bioinspired bottom-up process was developed to produce self-assembled nanocomposites of cellulose synthesized by Acetobacter bacteria and native starch. This process takes advantage of the way some bacteria extrude cellulose nanofibres and of the transport process that occurs during the gelatinization of starch. Potato and corn starch were added into the culture medium and partially gelatinized in order to allow the cellulose nanofibrils to grow in the presence of a starch phase. The bacterial cellulose (BC)–starch gels were hot pressed into sheets that had a BC volume fraction higher than 90%. During this step starch was forced to further penetrate the BC network. The self-assem…

Synthesis and Properties of Amine-Cured Epoxy/Organophilic Layered Silicate Nanocomposites

Epoxy-layered silicate composites have been prepared by dispersing an organically modified montmorillonite (Nanofil 919) in an epoxy resin and curing in the presence of an aromatic hardener. Dispersion of the layered silicate within the epoxy matrix was verified using X-ray diffraction and transmission electron microscopy revealing that interaction improves upon organic silicate modification. Flexural properties and toughness increase with the organic silicate loading whereas glass transition temperature decreases and thermal stability remains practically unmodified.

Morphology, flexural, and thermal properties of sepiolite modified epoxy resins with different curing agents

A bisphenol A-based epoxy resin was modified with 5 wt% organically modified sepiolite (Pangel B40) and thermally cured using two different curing agents: an aliphatic diamine (Jeffamine D230, D230) and a cycloaliphatic diamine (3DCM). The morphology of the cured materials was established by scanning and transmission electron microscopy analysis. The thermal stability, thermo-mechanical properties, and flexural behaviour of the sepiolite-modified matrices were evaluated and compared with the corresponding neat matrix. The initial thermal decomposition temperature did not change with the addition of sepiolite. The flexural modulus of the epoxy matrix slightly increases by the incorporation o…

Separation Efficiency of Two SEC Packings: Comparison of Chromatographic, Thermodynamic, and Fractal Parameters

Abstract The size‐exclusion chromatographic (SEC), thermodynamic, and fractal behavior of two organic packings, named TSK‐Gel HHR and TSK‐Gel HXL, has been compared in order to assess their separation efficiency. The different experimental elution trends of five solvent/polymer systems have been evidenced through the universal calibration curves, and the existence of secondary mechanisms (such as adsorption) has been quantified by the chromatographic partition coefficient K p. From a thermodynamic point of view, the swelling and crosslinking degrees have been evaluated and compared in the two gels assayed. Moreover, the values of some fractal parameters (fractal dimension of the surface and…

Monitoring molecular dynamics of bacterial cellulose composites reinforced with graphene oxide by carboxymethyl cellulose addition

[EN] Broadband Dielectric Relaxation Spectroscopy was performed to study the molecular dynamics of dried Bacterial Cellulose/Carboxymethyl Cellulose-Graphene Oxide (BC/CMC-GO) composites as a function of the concentration of CMC in the culture media. At low temperature the dielectric spectra are dominated by a dipolar process labelled as a beta -relaxation, whereas electrode polarization and the contribution of dc-conductivity dominate the spectra at high temperatures and low frequency. The CMC concentration affects the morphological structure of cellulose and subsequently alters its physical properties. X-ray diffractometry measurements show that increasing the concentration of CMC promote…

A thermodynamic analysis on the coincidence of extrema conditions in the sorption equilibrium for ternary polymer systems

Flory-Huggins theory of polymer solutions has been used to express the condition of extrema values in the total sorption, as well as the inversion point in the preferential adsorption parameters for termary polymer systems. Two approaches have been followed, the first considers the binary and ternary interaction parameters independent of polymer concentration and solvent composition. In the second one, this dependence has been introduced. Our attention is focused on the volume fraction of solvent mixture dependence of the above parameters, in order to confirm or not the coincidence between the extrema values and the inversion point. Several cosolvent and cononsolvent ternary polymer systems…

Viscometric behaviour of polymer blends based on poly (vinylidene fluoride)

The viscosity behaviour of dilute dimethylformamide solutions of poly(vinylidene fluoride)-poly (methyl methacrylate) and poly(vinylidene fluoride)-polystyrene has been studied at 25°C. The polymer concentration ranges are such that neither phase separation nor microgel formation occurs, although we are very close to theta conditions. The intrinsic viscosity and viscosity interaction parameter of the ternary mixtures have been calculated. The estimation of the compatibility of the above polymer pairs has been studied based on: a) specific viscosities; b) viscosity interaction parameters, according to Krigbaum and Wall formalism, and c) viscosity interaction parameters of a system formed by …

Thermosetting composites based on bronze particles for archaeological and artistic metal heritage cloning

peer-reviewed Artificial Metals are polymeric semi-metallic composites obtained by combining thermosetting resins with atomized metal powders in order to achieve composite materials capable of reproducing metals, even in a rusty or corroded condition. These composites provide a solution for the reproduction of archaeological artefacts, sculptures, and ornaments for the purpose of conservation. This work explores mechanical properties of three different resins bronze composites loaded with two different proportions of metal filler. The degree of conversion of the samples was measured by differential scanning calorimetry (DSC) and flexural tests were carried out to determine their mechanical …

Thermodynamics of a polymer blend solution system studied by gel permeation chromatography and viscosity

Binary and ternary interaction parameters and their derivatives have been calculated with the Flory-Huggins formalism developed for a ternary polymer system. The equilibrium compositions of the ternary system tetrahydrofuran/polybutadiene/polystyrene that forms two phases in equilibrium at 25°C have been used to solve the binodal equations. With this set of parameters, the viscosimetric interaction parameters have been computed. For the sake of comparison, the experimental viscosimetric parameter has been determined from intrinsic viscosity data of a polymer (3) in a "binary solvent" (solvent + polymer (2)). It has been clearly shown that composition-dependent parameters are necessary to re…

A Qualitative Analysis of Secondary Mechanisms in SEC of Polymers Through the Mean Value of the Viscosimetric Exponent

Abstract Size exclusion chromatography (SEC) universal calibration curves for poly(dimethylsiloxane), polybutadiene and poly(2-vinylpyridine) samples have been obtained in columns packed with cross-linked polystyrene gel using cyclohexane, toluene, benzene, dioxane and tetrahydrofuran as eluents at 25°C. The eluents exhibit different thermodynamic quality for the polymeric solutes and for the gel matrix which is reflected in the values of their Mark-Houwink-Sakurada exponents a. The plots of log(hydrodynamic volume) versus retention volume for the polymeric solutes in different eluents are displaced to higher retention volumes than that of THF-polybutadiene (ideal SEC), evidencing the exist…

High Thermoelectric Power Factor Organic Thin Films through Combination of Nanotube Multilayer Assembly and Electrochemical Polymerization

In an effort to produce effective thermoelectric nanocomposites with multiwalled carbon nanotubes (MWCNT), layer-by-layer assembly was combined with electrochemical polymerization to create synergy that would produce a high power factor. Nanolayers of MWCNT stabilized with poly(diallyldimethylammonium chloride) or sodium deoxycholate were alternately deposited from water. Poly(3,4-ethylene dioxythiophene) [PEDOT] was then synthesized electrochemically by using this MWCNT-based multilayer thin film as the working electrode. Microscopic images show a homogeneous distribution of PEDOT around the MWCNT. The electrical resistance, conductivity (σ) and Seebeck coefficient (S) were measured before…

Controlling dielectrical properties of polymer blends through defined PEDOT nanostructures

[EN] The paper reports the crucial role of the morphology of poly(3,4-ethylenedioxythiophene) (PEDOT) nanostructures on the thermal and dielectric properties of polymer blends prepared thereof. PEDOT nanostructures with two different morphologies (nanoparticles and nanowires) were synthesized. The size for the nanoparticles was in the range 10 40 nm and the diameter of the nanowires was of ca. 200 nm. These nanostructures were blended with an insulating polymer matrix, poly(methyl methacrylate) (PMMA), to evaluate the dielectrical properties of the materials. The results of broadband dielèctric spectroscopy showed a strong correlation between the morphology of the nanostructure and the impr…

Modelling Monomer/Disc Composites Phase Behaviour

Summary: A model developed by Balazs' group to explain the phase behaviour of polymer/clay composites is extended to obtain an expression for the free energy of polymer/thin disc mixtures. Phase diagrams for monomer/disc mixtures are built by minimizing the free energy and calculating the chemical potentials of the three system components. Via the comparison of the diagrams, it is studied the effects of nanodisc size and interaction parameters on mixture stability and attained morphology. The performed predictions between monomers and discs give criteria that advance the properties of the mixture. Changes in monomer concentration and interaction parameters provide a means to prevent van der…

Cure kinetics of a cobalt catalysed dicyanate ester monomer in air and argon atmospheres from DSC data

A kinetic analysis of the cyclotrimerisation reaction of a dicyanate ester monomer catalysed by cobalt(II) acetylacetonate and nonylphenol in air and argon atmospheres has been carried out by differential scanning calorimetry (DSC). Dynamic and isothermal DSC scans as well as the glass transition temperature are the experimental data obtained. From isothermal scans a higher cyanate conversion in air than in argon was obtained. The cyanate conversions are satisfactorily described with a second-order kinetic equation in the kinetically controlled region, and by m-order (m<1) equation after vitrification is reached. Activation energies determined by different procedures agree among them, showi…

On the thermodynamic treatment of poly(vinylidene fluoride)/polystyrene blend under liquid—liquid phase separation conditions

Abstract This paper deals with experimental and theoretical investigations on the compatibility of binary of polymer blends in solution. The experimental phase boundary of a crystalline polymer such as poly(vinylidene fluoride) with polystyrene (an amorphous polymer) in dimethylformamide as solvent has been determined by size-exclusion chromatography at 25°C. The composition of the coexisting phases has been used to calculate interaction parameters by means of the Flory—Huggins-type function for the free energy of mixing, including composition dependence of the polymer-polymer interaction parameter and a first correction term denoted as ternary interaction parameter. The calculation of thes…

Ternary Polymer Solutions with Hydrogen Bonds, 1

The Flory Huggins methodology coupled to AET has been extended to ternary polymer systems, in particular to solvent (A)/polymer 1 (B)/polymer 2 (C) systems, with the two polymers displaying H-bonding interactions. Because the H-bonding can perturb the randomness of polymeric conformations, the change in Gibbs free energy of mixing, AG, should arise from changes in combinatorial entropy as well as in interaction energy. The combinatorial part of AG is evaluated through AET as a function of the association constant η between B and C components, the autoassociation constant a between B components, and the independent number m of interaction sites of acceptor C. The enthalpic contribution is ev…

TCNQ radical salts containing magnetic complexes: Different interaction modes of TCNQ with Copper tetraazamacrocycles

Abstract This work is devoted to the study of compounds [M(N 4 )](TCNQ) n , where N 4 = saturated or unsaturated tetraazamacrocycles, TCNQ= 7,7,8,8-tetracyanoquinodimethane, n= 2, 3. The metal is coordinated to two TCNQ groups only when there is coordinative unsaturation on it. When n= 2 all the TCNQ units are radical anions and no charge delocalization is observed. In the compounds with n= 3 only 2 3 of the TCNQ are negatively charged and a greater charge delocalization is possible. This delocalization only appears when none of the TCNQ's are coordinated to the metal and it is reflected in the higher conductivity values obtained in the solid state.

Preferential solvation of poly(methyl methacrylate) and a bisphenol A diglycidyl ether by size-exclusion chromatography

The preferential adsorption coefficient, lambda, of poly(methyl methacrylate), PMMA, in solutions formed by an epoxy resin in tetrahydrofuran (THF), was studied by size-exclusion chromatography (SEC). Only PMMA of lowest molar mass was preferentially solvated by epoxy but at low concentrations of epoxy in the mixture. At higher epoxy content PMMA was preferentially solvated by THF. A simultaneous and competitive solvation between the specific interactions PMMA-epoxy and the self association of epoxy at high concentrations would be the responsible of this inversion point. The more compacted coil of PMMA of higher molecular weights in solution could explain the lack of interaction of these po…

Viscometric study of mixtures of neutral and charged polymers in aqueous solution

The viscosity behaviour of aqueous mixtures formed by a polyelectrolyte (A) and a neutral polymer (B) such as polystyrene sulfonate (PSS)-polyvinylpyrrolidone (PVP) and polylysine (PLL)-PVP has been studied at 25°C. The intrinsic viscosity and viscosity interaction parameter of each polymer in water have been determined and have served us to estimate the compatibility of the different mixtures according to two different methodologies: (i) mixtures of two polymers in water as solvent and (ii) mixtures of either polymer A OFB in a solvent formed by either polymer B or A in water ("polymer solvent method"). By comparing the experimental and theoretical viscosity data it is clearly seen that: m…

Thermodynamic study on phase equilibrium of epoxy resin/thermoplastic blends

Abstract The experimental phase diagrams (cloud point curves) of three series of epoxy/thermoplastic blends, namely, epoxy/polystyrene (PS), epoxy/poly(ether sulfone) (PES), and epoxy/poly(ether imide) (PEI) as a function of molar mass and composition have been analysed from a thermodynamic point of view. A model based on the Flory–Huggins lattice theory considering the concentration dependence of the interaction parameter as predicted by Koningsveld was employed to determine the equilibrium compositions, and concentration and temperature dependent interaction parameters. Binodal, spinodal, and critical point data have been computed and show good agreement with experimental data.

Molecular dynamics of carrageenan composites reinforced with Cloisite Na+ montmorillonite nanoclay

[EN] Nanocomposites comprising biodegradable carrageenan and glycerol(KCg) as the host polymer, with different contents of natural montmorillonite (MMT) as filler, were prepared by a solution casting process. Different techniques have been used to determine the interaction/behavior among the different components of the samples such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Transmission electron microscope (TEM) and, mainly, Dielectric relaxation spectroscopy (DRS). FTIR indicates hydrogen interaction between carrageenan matrix and silicate that is confirmed by the XRD data indicating some kind of carrageenan intercalation between the MMT layers. A rather ho…

A procedure for predicting sorption equilibrium in ternary polymer systems from Flory–Huggins binary interaction parameters and the inversion point of preferential solvation

A procedure has been developed, based on the Flory–Huggins theory as generalized by Pouchlý, which permits the calculation of preferential (λ) and total (Y) sorption coefficients from previous information on the binary interaction parameters, χ, χ, and g12(ϕ10) and on the mixture composition at which the sign of λ inverts. The expressions obtained were applied to 10 cosolvent polymer systems for which experimental values of λ and Y are known. Practically in all the studied systems, the theoretical predictions are in fair accordance with the experimental data.

Interaction of quinine with negatively charged lipid vesicles studied by fluorescence spectroscopy Influence of the pH

Abstract The interaction of quinine with dimyristoylphosphatidic acid (DMPA) and dimyristoylphosphatidyl glycerol (DMPG) small unilamellar vesicles in the gel phase was studied by steady-state fluorescence spectroscopy at pHs 7, 6, 5 and 4 and 20°C. In aqueous solution, with excitation at 335 nm, the emission fluorescence spectrum of quinine varied with pH reflecting the occurrence of different charged species of the drug. In all cases, the emission maximum centered at 383 or 443 nm shifted to lower wavelength in the presence of vesicles. This indicates that the membrane-bound state quinine is in an environment of low polarity. Drug monocationic species were deeply buried in DMPG relative t…

Viscoelastic behavior of epoxy prepolymer/organophilic montmorillonite dispersions

Dispersions of a bisphenol A-based epoxy resin with an organophilic montmorillonite (Nanofil 919) were studied by X-ray diffraction and oscillatory shear rheometry. X-ray studies reveal that the clay is intercalated by the epoxy and forms stable dispersions. The viscoelastic behavior of the nanodispersions was measured as a function of the Nanofil concentration and temperature. An increase in both G′ and G″ moduli was detected as the concentration increases. Furthermore, a transition from a liquid-like behavior, at low temperatures, to a solid-like behavior, at higher temperatures, was observed for all the samples. This transition is accounted for the formation of a percolated structure of …

A Flory–Huggins thermodynamic approach for predicting sorption equilibrium in ternary polymer systems

The Flory–Huggins theory as modified by Pouchlý has been applied to calculate preferential (λ) and total (Y) sorption coefficients for a ternary polymer system. The ternary interaction function (ϕ1ϕ2ϕ3GT(u1, ϕ3)) is described as the product of three independent binary functions. This expression allows prediction of λ and Y from binary interaction parameters χ, χ, g, g, and g12(ϕ10). Three ternary polymer systems are used to check the validity of the expression. Moreover for polymer systems in which the parameters g and/or g are unknown, a procedure to evaluate them has been developed and verified on systems for which sufficient experimental information is available.

Cover Picture: Macromol. Theory Simul. 1/2007

An experimental study of dynamic behaviour of graphite polycarbonatediol polyurethane composites for protective coatings

Segmented polycarbonatediol polyurethane (PUPH) has been synthesized and modified with different amounts of graphite conductive filler (from 0 to 50 wt%). Thermal and dynamical thermal analysis of the composites clearly indicates changes in the polyurethane relaxations upon addition of graphite. Broadband dielectric spectroscopy has been used to study the dielectric properties of the (PUPH) and one composite in the frequency range from 10−2 to 107 Hz and in the temperature window of −140 to 170 ◦C. Relaxation processes associated with different molecular motions and conductivity phenomena (Maxwell–Wagner–Sillars and electrode polarization) are discussed and related to the graphite content

Controlling the thermoelectric properties of polymers: application to PEDOT and polypyrrole

Poly(3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole (PPy) films have been prepared by an electrochemical method in a three electrode cell. The films have been obtained at different oxidation levels regarded as bipolaron, polaron and neutral states by varying the voltage, as is usually done in conjugated heterocyclic polymers. The voltage (-0.2V1.0 V) has been applied versus a Ag/AgCl reference electrode, producing a variation of one order of magnitude in the electrical conductivity and the Seebeck coefficient of the films. In the voltage range explored, the electrical conductivity increases from 80 to 766 S cm(-1) in PEDOT and from 15 to 160 S cm(-1) in PPy, while the Seebeck coefficie…

Effect of chain extender on the morphology, thermal, viscoelastic, and dielectric behavior of soybean polyurethane

An Analysis of the Concentration Effects on Elution Volumes by Using the Preferential Solvation Parameter in Two SEC Packings

Size exclusion chromatography (SEC) elution behavior of different solvent/polymer systems has been analyzed from chromatographic, thermodynamic, and hydrodynamic points of view in two organic column packings based on polystyrene/divinylbenzene (PS/DVB) copolymer, μ-styragel and TSK-Gel H HR . Although both packings present similar chromatographic properties, some differences arise when eluting the same systems. The values of the adsorption distribution coefficients, K p , have been correlated with the preferential solvation coefficient, λ (see Figure), for both packings, showing that those systems with lower and negative λ values (denoting higher preferential solvation of the polymer by the…

Comparative evaluation of the swelling and degrees of cross-linking in three organic gel packings for SEC through some geometric parameters.

Abstract The size exclusion chromatographic (SEC) behavior of five solvent/polymer systems in three organic column packings based on polystyrene/divinylbenzene (PS/DVB) copolymer, TSK-Gel H HR , μ-styragel and TSK-Gel H XL , has been compared. All the packings offer similar characteristics (pore size, particle size and efficiency) but some differences have been found when eluting the same systems. The different elution behavior observed in both polymeric gels has been analyzed in terms of their swelling and cross-linking degrees and of the fractal parameters. From the Universal Calibration plots, values of the chromatographic partition coefficient, K p , have been obtained and using some eq…

Interaction of Quinine with Model Lipid Membranes of Different Compositions

The binding of a drug such as Quinine with neutral and negatively charged small unilamellar lipid vesicles at pH 7 and 37 degrees C was investigated. Changes in the fluorescence properties of the drug after association with the liposomes were used to obtain binding isotherms over a range of phospholipid compositions at different ionic strengths. Under such conditions, the association was strongly enhanced by the negative net charge of the bilayer but diminished by the increasing presence of electrolytes in the aqueous media. Binding data were analyzed in terms of a surface partition equilibrium without and after correcting for electrostatic effects by means of the Gouy-Chapman theory. The i…

Characterization of the nanocomposite laminate structure occurring in fish scales from Arapaima Gigas

In the present paper, the nanocomposite laminate structure of scales from the Amazonian fish Arapaima Gigas is investigated. The structure and composition of the scales were assessed by means of X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FTIR). The theory of Fickian diffusion is used and discussed in order to rationalize the water absorption and desorption behavior of the scales. Morphology studies and fracture analysis of the native scales were carried out using Transmission Electron Microscopy (TEM), Light Optical Microscopy (LOM) and Scanning Electron Microscopy (SEM). A fibrous layer of collagen and a plywood-like structure were observed. In order to study the …

A comparative study between cosolvent and cononsolvent ternary polymer systems through the preferential adsorption coefficient

Sorption equilibrium of polystyrene and poly (dimethyl siloxane) in mixed solvents has been monitored by means of the preferential adsorption coefficient experimentally determined from intensity light scattering measurements. The pairs of solvents used to dissolve each polymer sample have been selected for the purpose to perform cosolvent and cononsolvent ternary polymer systems. Flory-Huggins formalism including ternary interactions has been used to predict the sorption equilibrium for the cosolvent system and, for the first time, for cononsolvent ones. Moreover, the proportionality between binary and ternary interactions, recognized by Pouchly, is also corroborated for both ternary polyme…

Effect of Chitin Whiskers on the Molecular Dynamics of Carrageenan-Based Nanocomposites

[EN] Films of carrageenan (KC) and glycerol (g) with different contents of chitin nanowhiskers (CHW) were prepared by a solution casting process. The molecular dynamics of pure carrageenan (KC), carrageenan/glycerol (KCg) and KCg with different quantities of CHWs as a filler was studied using dielectric relaxation spectroscopy. The analysis of the CHW effect on the molecular mobility at the glass transition, T-g, indicates that non-attractive intermolecular interactions between KCg and CHW occur. The fragility index increased upon CHW incorporation, due to a reduction in the polymer chains mobility produced by the CHW confinement of the KCg network. The apparent activation energy associated…

Binding of basic amphipathic peptides to neutral phospholipid membranes: a thermodynamic study applied to dansyl-labeled melittin and substance P analogues.

A thermodynamic approach is proposed to quantitatively analyze the binding isotherms of peptides to model membranes as a function of one adjustable parameter, the actual peptide charge in solution z(p)+. The main features of this approach are a theoretical expression for the partition coefficient calculated from the molar free energies of the peptide in the aqueous and lipid phases, an equation proposed by S. Stankowski [(1991) Biophysical Journal, Vol. 60, p. 341] to evaluate the activity coefficient of the peptide in the lipid phase, and the Debye-Huckel equation that quantifies the activity coefficient of the peptide in the aqueous phase. To assess the validity of this approach we have s…

FTIR isothermal cure kinetics and morphology of dicyanate ester resin/polysulfone blends

Abstract The isothermal cure of a dicyanate ester monomer by “in situ” Fourier transform infrared spectroscopy (FTIR) has been investigated. The degree of cyanate conversion and the kinetic parameters have been determined for cobalt catalyzed and uncatalyzed resin as well as for polysulfone (PSF) modified systems at different curing temperatures. The cyanate conversion increases with the increment of temperature and with the addition of a catalyst, but it does not vary with the addition of PSF. In all the systems studied, the rate of reaction showed a second-order dependence on the cyanate concentration in the kinetically controlled stage. Moreover, the addition of PSF generates a matrix wi…

Morphology and thermal behavior of dicyanate ester-polyetherimide semi-IPNS cured at different conditions

A high-temperature thermosetting bisphenol-A dicyanate, BADCy was modified with polyetherimide, PEI, at various compositions. Phase separation and rheokinetics through curing were studied by optical microscopy, dynamic and isothermal differential scanning calorimetry, and rheological measurements. The PEI phase separated at the early stages of curing, well before gelation, and did not affect the polycyclotrimerization kinetics. The phase structure and thermal properties of the final network were investigated as a function of the PEI content and cure temperature. For this purpose, dynamic mechanical analysis, scanning electron microscopy studies, and thermogravimetrical analysis were carried…

Prediction of maxima and minima in the curve of total sorption parameter in ternary polymer systems. Influence of ternary interaction parameter

Flory-Huggins theory modified by Pouchly has been applied to predict maxima and minima in the curve of total sorption in ternary polymer systems formed by a polymer and two liquids. In this work, different diagrams based on experimental magnitudes easily obtained such as the difference in affinities of liquids, solvents and non solvents, and the solvent molar volume ratio. Total sorption parameter has been considered to be the decisive magnitude to define extrema conditions in both cosolvent and cononsolvent ternary polymer systems. The theoretical prediction is not altered by the inclusion of ternary interactions. Different examples of ternary systems dealing with vinyl polymers and polydi…

Electrochemical Synthesis of Hybrid Layered Thermoelectric Materials Based on PEDOT/SnS Doped with Ag

Binding of a fluorescent dansylcadaverine-substance P analogue to negatively charged phospholipid membranes.

Abstract We have investigated the binding of a new dansylcadaverine derivative of substance P (DNC-SP) with negatively charged small unilamellar vesicles composed of a mixture of phosphatidylcholine (PC) and either phosphatidylglycerol (PG) or phosphatidylserine (PS) using fluorescence spectroscopic techniques. The changes in fluorescence properties were used to obtain association isotherms at variable membrane negative charges and at different ionic strengths. The experimental association isotherms were analyzed using two binding approaches: (i) the Langmuir adsorption isotherm and the partition equilibrium model, that neglect the activity coefficients; and (ii) the partition equilibrium m…

Rheological study of gel phenomena during epoxide network formation in the presence of sepiolite

The dynamic behaviour during the crosslinking of an epoxy polymer near the gel point was monitored using rheological multiple frequency experiments. The influence of a needle-shaped inorganic nanofiller, sepiolite, either non-modified or organically surface modified during the cure process in the presence of an aliphatic and an aromatic hardener was investigated. The validity of various criteria for determining the gel point was examined for the crosslinking of these filled thermosets. The Winter–Chambon criterion at the gel point is obeyed by the unfilled and by the non-modified sepiolite-filled epoxy matrix with either of the two hardeners. However, physical gels are formed in the presenc…

ZnO-latex hybrids obtained by polymer-controlled crystallization: a spectroscopic investigation.

Micro- and submicrosized ZnO-polymer hybrid materials were synthesized by precipitating zinc oxide from an aqueous medium in the presence of poly(styrene-acrylic acid) latex nanoparticles, prepared by miniemulsion polymerization. Up to 10 wt % of the latex becomes incorporated into the crystals. Although the long-range order of the inorganic material is essentially not altered by the polymer, studies by photoluminescence (PL) spectroscopy and electron paramagnetic resonance (EPR) show that the latex particles influence the optical and paramagnetic properties of the hybrids, which can be correlated with changes in the defect structure. Typical PL emission spectra showed a narrow UV peak and …

Modelling the influence of nanoparticles in the phase behaviour of an epoxy/polystyrene mixture

Abstract The cloud point temperatures of four series of epoxy/polystyrene blends have been experimentally determined as a function of polymer mass and system composition. The phase diagrams show an UCST behaviour, increasing incompatibility as the molar mass increases. The Flory–Huggins theory with a concentration-dependent interaction parameter has been developed to study the compatibility of two polymers in presence of spherical nanoparticles. This theory has been first compared with the experimental cloud point curve in absence of nanoparticles, and secondly it has been used to predict the thermodynamic behaviour in presence of different volume fraction of nanoparticles. Nanoparticles co…

Predictability of properties of ternary systems solvent/solvent/polymer from interaction parameters of the binary systems—III. Analysis of binary potential functions forming ternary ones

Abstract The assumption that the ternary parameter, g τ , and its derivative with respect to polymer concentration, ( ∂g τ / ∂φ 3 ) μ 1 , φ 3 → 0 , can be described by three binary interaction parameters, g o i 3 ( i = 1, 2) and g 12 , implies that these must be independent functions. This feature has been demonstrated by using g o i 3 values obtained from A/B/polymer(P) and C/D/P ternary polymer systems to predict the ternary properties, namely preferential solvation (λ), second virial coefficient ( A 2 ) and intrinsic viscosity ([η]), of a A/C/P ternary system. Two distinct polymers, polystyrene(PS) and poly(dimethylsiloxane)(PDMS), have been utilized in three solvent mixtures, benzene(BZ…

Review on Polymers for Thermoelectric Applications.

In this review, we report the state-of-the-art of polymers in thermoelectricity. Classically, a number of inorganic compounds have been considered as the best thermoelectric materials. Since the prediction of the improvement of the figure of merit by means of electronic confinement in 1993, it has been improved by a factor of 3-4. In the mean time, organic materials, in particular intrinsically conducting polymers, had been considered as competitors of classical thermoelectrics, since their figure of merit has been improved several orders of magnitude in the last few years. We review here the evolution of the figure of merit or the power factor during the last years, and the best candidates…

Enhanced thermoelectric performance of PEDOT with different counter-ions optimized by chemical reduction

This work reports on the synthesis of the intrinsically conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with several counter-ions, ClO4, PF6 and bis(trifluoromethylsulfonyl)imide (BTFMSI), by electro-polymerization and its thermoelectric properties. We show that, depending on the counter-ion size, the thermoelectric efficiency of PEDOT can be increased up to two orders of magnitude. A further chemical reduction with hydrazine optimizes the power factor (PF). By changing the counter-ions, we were able to increase the electrical conductivity (σ) of PEDOT by a factor of three, while the Seebeck coefficient remains at the same order of magnitude in the three polymers. The best…

Ternary Polymer Solutions with Hydrogen Bonds, 2

Experimental ternary phase diagrams for ternary systems CHL/PS-MAA/PVPy with diverse MAA contents have been determined by GPC. The presence of MAA in the copolymers gives rise to specific interactions, by hydrogen bond formation between both polymeric components, so strong that the isotherm for the system with the highest MAA content so far studied, CHL/PS-MAA(8%)/PVPy, is representative of a complex coacervation situation. By applying the theoretical background deduced by coupling the Flory-Huggins lattice model to the AET developed for ternary polymeric systems SPP with specific intermolecular interactions (via hydrogen bonds), free energy surfaces for the CHL/PS-MAA/PVPy systems are cons…

Processing and Mechanical Properties of Natural Fiber Reinforced Thermoplastic Starch Biocomposites

Natural fiber reinforced starch polymers are processed by compression molding. Potato, sweet potato, and corn starch are used as matrices. Three types of natural fibers, namely sisal, jute, and cabuya, are used in concentrations varying from 2.5 to 12.5% w/w in the composites. Different plasticizers are used for the starch polymers, such as water and glycerol. Mechanical properties are assessed by tensile and impact tests. In both cases, improved mechanical properties are obtained at increasing fiber contents. Tensile strength appears to be markedly improved with the addition of 10% by weight of sisal fibers, while the best results for impact strength are obtained for cabuya fibers.

Electrical conductivity properties of expanded graphite-polycarbonatediol polyurethane composites

Conductive polymer composites of segmented polycarbonatediol polyurethane and expanded graphite (EG) have been synthesized with different amounts of EG conductive filler (from 0 to 50 wt%). SEM, X-ray diffraction measurements, Fourier transform infrared and Raman spectroscopies demonstrated a homogeneous dispersion of the EG filler in the matrix. The dielectric permittivity of the composites showed an insulator to conductor percolation transition with increase in EG content. Significant changes in the dielectric permittivity take place when the weight fraction of EG is in the range 20–30 wt%. Special attention has been paid to the dependence of the conductivity on frequency, temperature and…

Enhanced polyurethanes based on different polycarbonatediols

Segmented thermoplastic polyurethanes (PUs) were prepared from 4,4′-diphenylmethane diisocyanate (MDI), 1,4-butanediol (BD) and different macrodiols with a molar mass of 1000. Properties of those PUs based on polycarbonatediol (PCD) were compared with their homologous based on polyesterdiol and polyetherdiol as macrodiols. The proportion used in this study was macrodiol:BD:MDI = 1:2:3, in mole ratio. The hard segment weight percentage is 48 wt% for different PUs. Thermogravimetric analysis, differential scanning calorimetry, differential mechanical analysis, Fourier transform infrared-attenuated total reflection spectroscopy, as well as mechanical properties and retention on flexural prope…

Deviations in the determination of the unperturbed dimensions of polymers arising in ternary polymer systems (solvent (1)/solvent (2)/polymer) can be explained by the inaccurate use of an interaction parameter independent of polymer molecular weight. On this basis, a new formalism for the calculation of the second virial coefficient from intrinsic viscosity is proposed. This formalism was tested (and compared with well established formalisms) for all ternary polymer systems with simultaneous intrinsic viscosity and second virial coefficient data in the literature.

The unperturbed dimensions parameter KΘ is one of the most important characteristics of a polymer chain. For binary systems (polymer/solvent) and mostly for ternary systems (polymer/solvent(1)/solvent(2)) the KΘ values show large discrepancies with respect to those under thetaconditions in a single solvent. These discrepancies can be explained by considering that the interaction parameter χ (and consequently the coil dimensions or the number of intramolecular contacts between polymer segments) changes with molecular weight M. Assuming this dependency, a modified Stockmayer-Fixman equation is proposed from which a unique value of KΘ for a given polymer, independent of M, is obtained. The use…

A fluorescence spectroscopy study of the interaction of monocationic quinine with phospholipid vesicles Effect of the ionic strength and lipid composition

Abstract The interaction of monocationic quinine with zwitterionic dimyristoyl phosphatidylcholine (DMPC) and mixed negatively-charged dimyristoylphosphatidyl glycerol (DMPG) DMPC small unilamellar vesicles in the liquid-crystalline phase was investigated by steady-state fluorescence spectroscopy at pH 7 and 37°C. The maximum fluorescence emission peak at 383 nm, upon excitation at 335 nm, shifts to lower wavelength and decreases its intensity as the ratio between the total lipid and quinine concentrations increases. This indicates that in the membrane-bound state quinine is in an environment of low polarity, more deeply buried when anionic DMPG is present in the vesicle. For monoprotonated…

Macromolecules in ordered media: 7. Influence of ionic strength and bilayer composition on the association of polyelectrolytes to mixed liposomes

The effect of both the phospholipid composition of the bilayer and the ionic strength of the medium on the association between poly(2-vinyl pyridine) and mixed liposomes based on dimyristoyl phosphatidic acid and dimyristoyl phosphatidil choline was investigated using fluorescence spectroscopy. Intensity changes upon addition of vesicles have allowed us to estimate the extent of the association and data have been processed as association isotherms. We found that the association is enhanced by increasing both the ionic strength and the anionic phospholipid fraction. However, whereas the negative net charge of the bilayer strongly enhances the interaction, the presence of more and more electr…

Structure-property relationships of polycarbonate diol-based polyurethanes as a function of soft segment content and molar mass

Segmented thermoplastic polyurethanes (PUs) have been synthesized with polycarbonate diol as soft segment and 4,4′-diphenylmethane diisocyanate and butanediol as hard segment. Two different series employing two different soft-segment molar mass, 1000 and 2000 g/mol, and by changing the hard-segment content from 32 to 67% have been investigated with the aim to elucidate the effect of the different content variations on the properties. Morphological, thermal, and mechanical properties have been studied by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), wide angle X-ray diffraction, atomic force microscopy, tensile and…

Poly(3,4-Ethylenedioxythiophene) nanoparticles as building blocks for hybrid thermoelectric flexible films

Hybrid thermoelectric flexible films based on poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles and carbon nanotubes were prepared by using layer-by-layer (LbL) assembly. The employed PEDOT nanoparticles were synthesized by oxidative miniemulsion polymerization by using iron(III) p-toluenesulfonate hexahydrate (FeTos) as an oxidant and poly(diallyldimethylammonium chloride) (PDADMAC) as stabilizer. Sodium deoxycholate (DOC) was used as a stabilizer to prepare the aqueous dispersions of the carbon nanotubes. Hybrid thermoelectric films were finally prepared with different monomer/oxidant molar ratios and different types of carbon nanotubes, aiming to maximize the power factor (PF). The …

Three dimensional PEDOT nanowires network

Abstract A three dimensional (3D) structure of poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires have been prepared by electrochemical polymerization using 3D-alumina templates. The templates were synthesized by pulse anodization in an electrochemical bath. A 3D free standing network has been obtained after the template removal. The morphological analysis by electron microscopy shows the existence of a 3D PEDOT nanowires network whose nanowire diameter is around 20 nm for the vertical nanowires and 10 nm for the transversal connections. Electrical properties such as the I–V characteristics and the Seebeck coefficient were studied for the nanowires network. Also, the optical properties have…

Kinetic parameters of a cyanate ester resin catalyzed with different proportions of nonylphenol and cobalt acetylacetonate catalyst

The isothermal cure of a dicyanate ester monomer has been investigated by differential scanning calorimetry (DSC) in the presence of different quantities of a catalyst system formed by nonylphenol (NP) and cobalt (II) acetylacetonate (Co(AcAc)2). Two sets of experiences were studied. Firstly, the NP composition was varied from 0 to 10 per hundred resin (phr) and secondly, the Co(AcAc)2 loadings were changed at 2 phr of NP. It has been observed that the cyanate conversion increases significantly after the first addition of the metal catalyst and, also, at the same time the thermal stability improves. Moreover, the kinetic data have been fitted with a second-order equation respect to the cyan…

Nanocomposites of bacterial cellulose/hydroxyapatite for biomedical applications.

In the present work, a nanocomposite material formed by bacterial cellulose (BC) networks and calcium-deficient hydroxyapatite (HAp) powders was synthesized and characterized. The HAp nanoparticles were previously prepared by a wet chemical precipitation method, starting from aqueous solutions of calcium nitrate and di-ammonium phosphate salts. Energy-dispersive spectroscopy reveals that the prepared HAp corresponds to calcium-deficient hydroxyapatite. BC-HAp nanocomposites were prepared by introducing carboxymethylcellulose (CMC) into the bacteria culture media. HAp nanoparticles were then introduced and remained suspended in the culture medium during the formation of cellulose nanofibrils…

Estimation of the Compatibility Between Poly(Methylmethacrylate) and Poly(Styrene Co Vinyl Phenol) Blends from Dilute Solution Measurements

Abstract The compatibility of poly(methyl methacrylate) (PMMA) with poly(styrene‐co‐vinyl phenol) (PS‐VPh) with two different contents of vinyl phenol, 5.8 and 7.2%, in dilute tetrahydrofuran solutions has been investigated by size exclusion chromatography and fluorescence spectroscopy at 25°C. The chromatographic technique permits the evaluation of the preferential solvation at different PMMA/PS‐VPh ratios. Changes in the fluorescence properties of PS‐VPh, caused by its association with PMMA, were used to obtain the fraction of copolymer bound to PMMA at diverse PMMA compositions. Both techniques agree quantitatively in every system, indicating that the association increases when the PMMA …

Interactions of quinine with polyacrylic and poly-L-glutamic acids in aqueous solutions

Abstract Drug-loaded polymers provide an attractive form for controlled drug delivery systems. A proper knowledge of polymer–drug interactions can aid in the designing of polymers for various drug-delivery applications. In this paper we have investigated the interaction of a drug such as quinine, with synthetic macromolecules such as poly(acrylic acid), PAA, and poly(L-glutamic acid), PGA, at pH 7 and 37 °C by fluorescence spectroscopy and viscometry. The analysis of the binding isotherms revealed that the association process is positive cooperative up to a threshold concentration and then it is negative. In addition, the thermodynamic parameters vary along the isotherm. Results also sugges…

Viscometric study on the compatibility of polymer–polymer mixtures in solution

Abstract The viscosity behaviour of mixtures formed by two uncharged polymers in dilute solution has been studied at 25°C. The ternary systems assayed, and denoted solvent (1)/ polymer (2)/ polymer (3), have in common the poly(ether sulphone) (PES) as polymer 2, and poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA) or poly(styrene) (PS) as polymer 3. The intrinsic viscosity and the viscometric interaction parameters have been experimentally measured for the binary (solvent/polymer) as well as for the ternary systems, and also theoretically evaluated for the latter. The estimation of the compatibility degree of the above polymer pairs have been done by means of three criteri…

In Situ Synthesis of Conducting Polymers: A Novel Approach toward Polymer Thermoelectrics

The efficient conversion of thermal energy into electricity by means of durable and scalable solid-state thermoelectric devices has been a well stablished aim. Electrically conducting polymers have...

An Approach on the Hydrogen Absorption in Carbon Black after Gamma Irradiation

In this work, different samples of an industrial carbon black are used to study the hydrogen intake from an over pres-surized atmosphere and its changes due to alteration of its level of crystallinity produced by ¿-irradiation. The monitor-ing of the hydrogen adsorption was made by means of thermogravimetric analysis and by measurements of some elec-trical parameters as the Seebeck coefficient. X-ray diffraction shows that the irradiation diminishes the level of crystal-line perfection. These results show interesting possibilities to use carbon black as cheap hydrogen absorbers.

Sepiolite-reinforced epoxy nanocomposites: Thermal, mechanical, and morphological behavior

A bisphenol A-based epoxy resin was modified with pristine sepiolite and an organically surface-modified sepiolite and thermally cured using two different curing agents: an aliphatic and a cycloaromatic diamine. The nanocomposites were characterized by dynamic mechanical analysis (DMA), rheology, thermogravimetric analysis (TGA), and electron microscopy. The initial sepiolite–epoxy mixtures show a better dispersion for the sepiolite-modified system that forms a percolation network structure. Mechanical properties have also been determined. The flexural modulus of the epoxy matrix slightly increases by the incorporation of the organophilic sepiolite. The flexural strength of the sepiolite-mo…

PEDOT thin films with n-type thermopower

peer-reviewed Synthesis of n-type organic semiconductors is challenging as reduced states are difficult to obtain due to their instability in air. Here, we report tailoring of semiconducting behavior through control of surfactant concentration during synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles. Nanoparticles were synthesized by mini-emulsion polymerization, where stable suspensions were used to produce polymer films by a simple casting technique on polyethylene terephthalate (PET) substrates. Electrical conductivity and Seebeck coefficients were measured as a function of surfactant concentration. It was found that conductivity decreases three orders of magnitude as s…

Thermal sensor based on a polymer nanofilm

In this work, we have developed a thermal sensor based on poly(3,4 ethylenedioxythiophene) (PEDOT) nanofilms as thermoelectric material. The PEDOT nanofilms have been synthesized by the electrochemical polymerization method. The thicknesses of the films were around 120 nm. The doping level of PEDOT was controlled by chemical reduction using hydrazine. The achieved Seebeck coeficient is 40 uV/K. A PEDOT nanofilm was integrated into an electronic circuit that amplifies the voltage originated from the Seebeck effect. The temperature increment produced by a fingerprint touching the film is enough to switch on a light emitting diode. Peer Reviewed

Modeling Studies of the Phase Behavior of Monomer/Polymer/Disk Composites

The model developed by Balazs et al. to explain the phase behavior of polymer/clay composites is extended to monomer/polymer/clay composites, obtaining an expression for the free energy of a monomer/polymer/thin-disk mixture. By minimizing the free energy and calculating the chemical potentials of the three system components, phase diagrams for the monomer/disk and monomer/polymer/disk mixtures are contructed. Through the evolution and comparison of these diagrams, the effects of nanodisk size, polymer molecular mass and interaction parameters (temperature) on mixture stability and attained morphology are then studied.

Hybrids composites of NCCO/PEDOT for thermoelectric applications

Abstract Organic materials are becoming a realistic roadway to fabricate efficient thermoelectric devices using environmental friendly materials. Such requirements are actually fulfilled by thermoelectric generators operating by conducting polymers, but also by hybrid materials. The combination of organic + inorganic compounds may exhibit a high electrical conductivity and Seebeck coefficient as well as lower thermal conductivity in order to efficiently generate thermoelectric power. In these hybrid compounds, perovskite-type oxides are a suitable election for the inorganic part since they have a high Seebeck coefficient although their electrical conductivity is usually low. Blending them w…

In Situ Synthesis of Polythiophene and Silver Nanoparticles within a PMMA Matrix: A Nanocomposite Approach to Thermoelectrics

The processability of organic thermoelectric materials plays a crucial role due to their clear advantages of applicability in large-scale areas compared to traditional inorganic counterparts. A promising way to process thermoelectric materials based on conductive polymers is through in situ polymerization in an insulating polymer matrix. This work shows an interpenetrating polymeric network based on polythiophene, silver nanoparticles (Ag NPs), and poly(methyl methacrylate) (PMMA) produced by the oxidative polymerization of terthiophene by an oxidizing silver salt in a PMMA matrix. Ag NPs are in situ synthesized simultaneously as a byproduct. The reaction occurs very fast in the solid state…

Optimization of Cell Growth on Bacterial Cellulose by Adsorption of Collagen and Poly-L-Lysine

Poly-L-lysine and collagen were separately added to bacterial cellulose (BC) nanofibers. The ionic surface charge had been previously modified in order to promote the adsorption of poly-L-lysine and collagen. Cell adhesion of Chinese hamster ovary (CHO) cells on BC surfaces was confirmed by removing unattached cells from the BC substrates. Cell viability was calculated and it was determined that both poly-L-lysine-BC and collagen-BC substrates are viable for cell growth. The results showed that the cell viability in poly-L-lysine modified BC substrate is similar to the one observed in polystyrene tissue culture plates.

Electrochemical Synthesis of an Organic Thermoelectric Power Generator.

[EN] Energy harvesting through residual heat is considered one of the most promising ways to power wearable devices. In this work, thermoelectric textiles were prepared by coating the fabrics, first with multiple-wall carbon nanotubes (MWCNTs) by using the layer-by-layer technique and second with poly(3,4-ethylenedioxythiophene) (PEDOT) deposited by electrochemical polymerization. Sodium deoxycholate and poly(diallyldimethylammonium chloride) were used as stabilizers to prepare the aqueous dispersions of MWCNTs. The electrochemical deposition of PEDOT on the MWCNT-coated fabric was carried out in a three-electrode electrochemical cell. The polymerization of PEDOT on the fabric increased the…

Properties and structure of cyanate ester/polysulfone/organoclay nanocomposites

In this paper, a cyanate ester (CE) matrix has been modified with polysulfone and an organic montmorillonite (Nanofil 919). The blend was thermally cured in presence of copper acetylcetonate and nonylphenol. The morphology of the cured materials was investigated by wide angle X-ray, scanning and transmission electron microscopy techniques. An intercalate structure of silicate platelets in the cyanate matrix has been obtained. Furthermore, results of thermogravimetric analysis (TGA) suggest that CE/PSF/Nanofil 919 nanocomposites have higher thermal stability than the neat resin, increasing the onset decomposition temperature. Flexural strength distributions of modified and neat cyanate matri…

Surface-Functionalized Latex Particles as Controlling Agents for the Mineralization of Zinc Oxide in Aqueous Medium

Polystyrene latex particles modified at the surface with different hydrophilic functional groups were prepared by miniemulsion polymerization and used as controlling agents in the crystallization of zinc oxide from aqueous medium. The effects of the chemical nature of the surface functionalization and the latex concentration on the crystal growth, morphology, and crystalline structure of the resulting zinc oxide were analyzed. Micro- and submicrosized crystals with a broad variety of morphologies depending on the functionalization were obtained. Among the different latexes studied, the acrylic-acid-derived particles were shown to be a convenient system for further quantitative investigation…

Investigation of compatibility of a dicyanate ester monomer and polysulfone by size-exclusion chromatography and viscometry

The influence of solvent on the compatibility behaviour of Arocy B10, a cyanate ester monomer, and polysulfone (PSF) was investigated by means of dilute solution viscometry and of the preferential solvation parameter at 25 °C. The ternary systems under study are: tetrahydrofuran/Arocy B10/polysulfone (PSF), N,N-dimethylformamide/Arocy B10/PSF and dichloromethane/Arocy B10/PSF. Values of the specific viscosity of PSF in a ‘binary solvent’ formed by Arocy B10 + solvent have been used to determine the compatibility of the polymer blend Arocy B10/PSF. An interaction parameter Δb that depends on concentration has been determined. The preferential solvation parameter was measured by size-exclusio…

Macromolecules in ordered media. II. A fluorescence study of the polymer-liposome association

The interactions of poly (4-vinyl pyridine) with dimyristoylphosphatidic acid-based liposomes were studied in heterogeneous solution systems. The polymer was dispersed in aqueous buffer solutions of small unilamellar vesicles and after a suitable period of incubation to raise the equilibrium, the experiments has been conducted as a function of polymer concentration and temperature. According to the measurements of the steady-state fluorescence spectra, changes in the intensities as well as shifts in the emission peak wavelength, has served as raw data to accounting for the polymer-vesicle interactions. Quantitative evaluation of the interaction has been done using a simple associating model…

Manufacturing Te/PEDOT Films for Thermoelectric Applications

In this work, flexible Te films have been synthesized by electrochemical deposition using PEDOT [poly(3,4-ethylenedioxythiophene)] nanofilms as working electrodes. The Te electrodeposition time was varied to find the best thermoelectric properties of the Te/PEDOT double layers. To show the high quality of the Te films grown on PEDOT, the samples were analyzed by Raman spectroscopy, showing the three Raman active modes of Te: E1, A1, and E2. The X-ray diffraction spectra also confirmed the presence of crystalline Te on top of the PEDOT films. The morphology of the Te/PEDOT films was studied using scanning electron microscopy, showing a homogeneous distribution of Te along the film. Also an a…

Changes in the thermoelectric response of vitreous carbon due to the irradiation by γ-rays

In order to study variations in the thermoelectric properties, some commercial glassy carbon samples were subjected to a sequence of steps consisting of a combination of irradiation with γ-rays produced by radioisotopes 60Co, and hydrogen adsorption when the samples were put in an over pressured atmosphere of this gas. With this procedure it was possible to observe that the irradiation decreases the electrical conductivity of glassy carbon samples and the hydrogenation changes the sign of Seebeck coefficient. The material initially is an n-type semiconductor, but with hydrogenation changes to p-type semiconductor. X-ray diffraction analysis showed that the hydrogenated vitreous carbon is mo…

Preferential solvation of a dicyanate ester monomer and poly(sulfone) in different organic solvents by size-exclusion chromatography.

Preferential solvation parameters A in the ternary systems solvent (1) -monomer (2) -polymer (3) were determined as a tool to measure the compatibility between the cyanate ester monomer Arocy B10 and poly(sulfone), PSF, in the presence of three organic solvents: tetrahydrofuran, dimethylformamide and dicloromethane. The A parameter was measured by size-exclusion chromatography at different monomer-to-polymer ratios. The quantitative evaluation was rigorously made at polymer-diluted conditions. PSF was found to be preferentially solvated by the monomer. Concerning the solvent used, systems containing tetrahydrofuran showed the strongest solvation, the lowest A values being those obtained in …

Thermal and Structural Analysis of Natural Fiber Reinforced Starch-Based Biocomposites

This is the second part of a series of articles dealing with characterization of starch based biodegradable composites. Potato, sweet potato, and corn starch varieties were used as matrices of the biocomposites. Natural fibers including jute, sisal, and cabuya were used as discrete reinforcement. Water and glycols were used as plasticizers. Compression molded specimens were prepared and characterized by a variety of techniques. Differential Scanning Calorimetry (DSC) and Thermogravimetry (TGA) were used to characterize the thermal behavior of these composites. Processed specimens did not show the typical endothermic peak observed in DSC scans for native starch powder. No significant differe…

Evaluation of thermodynamic parameters for blends of polyethersulfone and poly(methyl methacrylate) or polystyrene in dimethylformamide

Liquid-liquid phase separation phenomena have been investigated for a ternary system containing two polymers and a solvent. Namely, dimethylformamide (DMF)/polyethersulfone (PES)/poly(methyl methacrylate) (PMMA) and DMF/PES/Polystyrene (PS). The composition of the three components in the two phases in equilibrium has been determined by size exclusion chromatographic (s.e.c.) analysis. The lattice-based mean-field theory, first developed by Flory and Huggins, has been modified to adequately describe these systems. In this respect, we have assumed that the parameters depend on the polymer concentration, and we have included a ternary parameter. The phase equilibrium compositions have been use…

La 1−xCaxMnO3 semiconducting nanostructures: morphology and thermoelectric properties

Semiconducting metallic oxides, especially perosvkite materials, are great candidates for thermoelectric applications due to several advantages over traditionally metallic alloys such as low production costs and high chemical stability at high temperatures. Nanostructuration can be the key to develop highly efficient thermoelectric materials. In this work, La 1−xCa x MnO3 perosvkite nanostructures with Ca as a dopant have been synthesized by the hydrothermal method to be used in thermoelectric applications at room temperature. Several heat treatments have been made in all samples, leading to a change in their morphology and thermoelectric properties. The best thermoelectric efficiency has b…

Reversible stress softening and stress recovery of cellulose networks

The mechanical properties of the plant cell wall play an important role in communication, differentiation and growth of plant cells. In particular, the expansive growth of plant cells is only possible because the material that forms the plant cell wall yields at a specific stress level, allowing for an increase in cell wall area. This process can be defined in mechanical terms as the relaxation of the wall stress. The current understanding of plant cell growth suggests that such relaxation behaviour occurs due to the presence of wall loosening agents rather than to the properties of the cellulose network itself. It is believed that certain nonenzymatic proteins, acting as wall loosening age…

Morphological Characterisation of Bacterial Cellulose-Starch Nanocomposites

Acetobacter sp. growing medium was modified in order to produce bacterial cellulose (BC) nanocomposites using a bottom-up technique that allowed starch to be introduced into the cellulose network. The BC-starch mats were hot-pressed to obtain nanocomposites sheets. Morphological characterisation was carried out using Atomic Force Microscopy and Environmental Scanning Electron Microscopy. The images obtained from microscopy were then processed using image analysis. Network properties, such as mesh size and fibre orientation were characterised. Fracture surfaces of these new nanocomposites were analysed.

Thermodynamic Study of Small Hydrophobic Ions at the Water–Lipid Interface

Abstract The thermodynamics of binding of two small hydrophobic ions such as norharman and tryptophan to neutral and negatively charged small unilamellar vesicles was investigated at pH 7.4 using fluorescence spectroscopy. Vesicles were formed at room temperature from dimyristoyl phosphatidylcholine (DMPC) or DMPC/dimyristoylphosphatidic acid and DMPC/dimyristoylphosphatidylglycerol. The changes in fluorescence properties were used to obtain association isotherms at variable membrane surface negative charge and at different ionic strengths. The binding of both ions was found to be quantitatively enhanced as the percentage of negative phospholipid increases in the membrane. Also, a decrease …

The intrinsic viscosities, [η], for the ternary systems alkane (1)/2-butanone (2)/poly(dimethylsiloxane) (PDMS)(3), with the alkanes decane, dodecane and hexadecane, are determined at 20,0°C. The constants a of the Mark-Houwink equation and the constant of the unperturbed dimensions, KΘ, of the polymer are evaluated over the whole composition range of the binary solvent mixture. [η] shows a pronounced maximum at intermediate compositions as found in cosolvent mixtures. In these cosolvent mixtures, the numerical values of KΘ are higher than in the single-component solvents, because the cosolvent mixtures correspond to a mixed solvent with an excess free energy, GE ≥ 0, the increase in KΘ bei…

Macromolecules in ordered media III. A fluorescence study on the association of poly-2-vinylpyridine with a phospholipid bilayer

Association of low molecular weight poly-2-vinylpyridine taken as a polycation model with unilamellar vesicles based on dimirystoylphosphatidic acid has been experimentally investigated by means of fluorescence energy transfer experiments. The conventional profiles for the binding isotherms were obtained, confirming strong deviations from the ideality of these complex fluid composites. Two approaches, named binding and partitioning equilibrium, respectively, were used to obtain the association constant, K A; the number of phospholipids that form a binding site, N; the partition coefficient, Λ; the activity coefficient, γ; and the effective charge, v. Analysis of these parameters as a functi…

Effects of Gamma Irradiation on the Kinetics of the Adsorption and Desorption of Hydrogen in Carbon Microfibres

In this study, three types of carbon fibres were used, they were ex-polyacrylonitrile carbon fibres with high bulk modulus, ex-polyacrylonitrile fibres with high strength, and vapour grown carbon fibres. All the samples were subjected to a hydrogen adsorption process at room temperature in an over-pressured atmosphere of 25 bars. The adsorption process was monitored through electrical resistivity measurements. As conditioning of the fibres, a chemical activation by acid etching followed by ¿-ray irradiation with 60Co radioisotopes was performed. The surface energy was deter-mined by means of the sessile drop test. Both conditioning treatments are supplementary; the chemical activation works…

Correlation between transport and equilibrium properties through the ternary interaction parameter for cosolvent and cononsolvent polymeric systems

A study of the ternary polymer systems dimethyl formamide-ethyl acetate-polystyrene, chloroform-1,4 dioxane-polystyrene and tetrahydrofuran-chloroform-polystyrene was carried out by viscosity and light scattering at 298 K. A good correlation has been found between the excess intrinsic viscosity, unperturbed polymer dimensions, second virial coefficient and the excess Gibbs free energy by using a ternary interaction parameter, dependent on molecular weight. This modification enables the conversion between transport and equilibrium properties.

Relative strength of H-bonding groups on biodegradable polymer-based blends in solution

The intermolecular hydrogen bonding interactions between poly(3-hydroxybutyrate) and poly(styrene-co-vinyl phenol) copolymers with mutual solvent epichlorohydrin were thoroughly investigated by steady-state fluorescence and viscosity techniques. Fluorescence spectroscopy along with viscosity technique was used to asses the intermolecular hydrogen bonding between poly-(3-hydroxybutyrate) and its blends with five copolymer samples of styrene–vinyl phenol, containing different proportions of vinyl phenol but similar average molecular weight and polydispersity index. In the case of very low OH contents (2–4 mol %), as expected, both components of poly(3-hydroxybutyrate) and poly(styrene-co-4-vi…