Fourier transform infrared studies of ionic interactions in perfluorinated acid copolymer blends

Ionic interactions have been shown to enhance polymer–polymer miscibility in several highly dissimilar blend systems. In some cases, the miscibility is due to proton transfer from an acidic site on one polymer to a basic site on another, which leads to ion–ion interactions. Studies that have focused on the formation of ionomer blends from highly dissimilar materials, such as fluorocarbons and hydrocarbons or aromatics and aliphatics of widely differing glass transitions, have shown that in the absence of ionic interactions, these materials are immiscible. In this study, we have used Fourier transform infrared (FTIR) spectroscopy techniques, both qualitatively and semiquantitatively, to evaluate the extent of the proton‐transfer mechanism in the enhancement of miscibility in perfluorinated acid copolymer/poly(ethyl acrylate) blends. The perfluorinated acid copolymer contains sulfonic acid groups, whereas the poly(ethyl acrylate) has been modified by the introduction of various amounts of 4‐vinyl pyridine groups as comonomers in the polymer chains. The proton‐transfer mechanism in this case consists of the transfer of the proton on the sulfonic acid group to the nitrogen on the pyridine group, forming a pyridinium cation and a sulfonate anion pair. FTIR has been used to distinguish between the pyridine and pyridinium groups through their absorption bands at 1416 and 1642 cm^?1, respectively. The relative intensities of these bands, as a function of the molar concentration of the pyridine comonomers in the blend, provides a direct quantitative indication of the extent of proton transfer occurring in the system. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1814–1823, 2003     

Electronic transport properties of polyaniline/PVC blends

The electrical conductivity and thermoelectric power of polyaniline/PVC blends was measured. Surprisingly, the conductivity of the blends is greater at low temperatures than that of the pure polyaniline sample. The conductivity follows approximately an exp (?T^?1/2) law over a considerable range of temperature, with deviations from this law observed at high temperature increases (with positive sign) except at very low temperatures, where negative peaks are observed. Possible models to interpret these observations are mentioned. © 1993 John Wiley & Sons, Inc.     

Mechanical properties of blends of PAMAM dendrimers with poly(vinyl chloride) and poly(vinyl acetate)

Hybrid blends of poly(amidoamine) PAMAM dendrimers with two linear high polymers, poly(vinyl chloride), PVC, and poly(vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonance (NMR) spectroscopy, and tensile property measurements. The data suggest a much higher degree of interaction between components of PVAc-containing blends compared to those containing PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2111–2117, 1998     

Conductivity and structure of melt‐processed polyaniline binary and ternary blends

In the present study, conductive binary and ternary blends containing polyaniline (PANI) were developed through melt blending. The binary blends' investigation focused on the morphology, in light of the components' interaction, and the resulting electrical conductivity. Similar solubility parameters of a given doped PANI and a matrix polymer lead to dispersion of fine PANI particles within the matrix, and to formation of conducting paths at low PANI contents. A plasticizer acting also as a compatibilizer improves the matrix polymer/PANI interactions. In ternary blends consisting of PANI and two immiscible polymers, the PANI preferrentially locates in one of the components, affecting the blend's morphology. This “concentrating” effect leads to relatively high electrical conductivity at a low PANI content. The electrical conductivity of the studied ternary blends is almost independent of the components' sequence of addition into the hot melt mixing device, exhibiting the selectivity of PANI towards one of the components. Copyright © 2000 John Wiley & Sons, Ltd.     

Preparation and characterization of polyaniline blends with polyvinyl acetate,polystyrene and polyvinyl chloride for toxic gas sensors

The conditions of processing and gas sensing of ­polyaniline (PANi) blends with polyvinyl acetate (PVAc), polystyrene (PS) and polyvinyl chloride (PVC) were investigated. Flexible, free‐standing and stretchable films of various blends compositions were obtained by casting. The mechanisms of the conducting blends response to a selection of gases and vapours were investigated using two techniques: measurement of conductance and mass changes using a four‐point probe method and X‐ray fluorescence (XRF) device, respectively. These responses to toxic gases and vapours are better explained by polymer blends than homopolymers. Prepared films were exposed to hydrogen halides, hydrogen cyanide, halogens, monochloroacetic acid (MCAA), 1‐3‐5 trichloromethyl benzene (TCMB), methylbenzyl bromide (MBB), bromoacetone (BA) and cyanogen bromide (CB). The changes in conductivity of various polymer frequently observed are partly due to one stage in the two‐stage sorption perhaps involving the swelling of the polymer and then diffusion of gases into polymer chains. The swelling of polymers is a slow process, therefore, we have pre‐swelled polymer films which tend to decrease the response times of blends in respect to gases. The structures of the blends are examined by STA (TGA & DSC) and SEM studies. Copyright © 2001 John Wiley & Sons, Ltd.     

Synthesis and characterization of a vinyl‐terminated benzoxazine monomer and its blends with poly(ethylene oxide)

A vinyl‐terminated benzoxazine (VB‐a), which could be polymerized through ring‐opening polymerization, was synthesized through the Mannich condensation of bisphenol A, formaldehyde, and allylamine. This VB‐a monomer was then subjected to blending with poly(ethylene oxide) (PEO), followed by thermal curing, to form poly(VB‐a)/PEO blends. The specific interactions, miscibility, morphology, and thermal properties of these blends were investigated with Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). Before curing, we found that PEO was miscible with VB‐a, as evidenced by the existence of a single composition‐dependent glass transition temperature (T_g) for each composition. The FTIR spectra revealed the presence of hydrogen‐bonding interactions between the hydroxyl groups of poly(VB‐a) and the ether groups of PEO. Indeed, the ring‐opening reaction and subsequent polymerization of the benzoxazine were facilitated significantly by the presence of PEO. After curing, DMA results indicated that the 50/50 poly(VB‐a)/PEO blend exhibited two values of T_g: one broad peak appeared in the lower temperature region, whereas the other (at ca. 327 °C, in the higher temperature region) was higher than that of pristine poly(VB‐a) (301 °C). The presence of two glass transitions in the blend suggested that this blend system was only partially miscible. Moreover, SEM micrographs indicated that the poly(VB‐a)/PEO blends were heterogeneous. The volume fraction of PEO in the blends had a strong effect on the morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 644–653, 2007     

Synthesis and characterization of new poly(azomethine ester)s having phenylthiourea units

New polyesters having azomethine and phenylthiourea groups in the polymer backbone were synthesized by interfacial polycondensation method. The dihydroxy monomer N-(4-hydroxy-3-methoxybenzal) N′-(4′-hydroxyphenyl)thiourea was condensed with six diacid chlorides: terephthaloyl, isophthaloyl, azeloyl, suberoyl, pimeloyl and adipolyl chlorides. The resulting polyesters were characterized by viscosity, IR, NMR and TGA analysis. The wholly aromatic poly(azomethine ester) derived from terephthaloyl chloride when blended with polyaniline/NH₄OH, polyaniline/HCl and pure polyaniline shows conductance in the range 3.2 × 10⁻³-0.91 × 10⁻¹ S cm⁻¹.     

Infrared characterization of poly(vinyl cinnamate) and its blends with poly(4-vinyl phenol) before and after UV exposure

The results of an infrared spectroscopic characterization of poly(vinyl cinnamate) (PVCIN) and its blends with poly(4-vinyl phenol) (PVPh) are reported before and after photo-crosslinking the PVCIN by exposure to UV radiation. The purpose of this article is to demonstrate methodology, and it is shown that quantitative analysis of the fraction of unsaturated ( CC ) double bonds, “free” (non-hydrogen bonded) and hydrogen bonded unsaturated ( CO CC ) and saturated ( CO C C ) acetoxy carbonyl groups is feasible in these blends as a function of UV exposure time. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1579–1590, 1998     

Synthesis and characterization of polyaniline doped with organic acids

Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004     

Synthesis,characterization, and blends of high temperature poly(arylether sulfone)s

The preparation of poly(4-oxy-1,4-phenylenesulfonyl-4,4′-biphenylene-4-sulfonylphenylene) (PBP) has been accomplished by the base mediated, polycondensation reaction between two biphenyl containing monomers. The bisphenol, 4,4′-bis[(4-hydroxyphenyl) sulfonyl]biphenyl (HSB), was reacted with 4,4′-bis[(4-chlorophenyl)sulfonyl]-biphenyl (CSB) in tetramethylene sulfone solvent. The highest mechanical properties and glass transition temperature was observed for polymer PBP with a reduced viscosity around 1.0 dL/g. Consequently, the current synthesis route provides polymer with higher properties than other historical preparative routes. Blends of PBP with a different poly(ether sulfone) were miscible based on the observance of a single glass transition temperature. The T_gs of the polymer blends exhibited an unusual positive deviation from the weighted linear averages of the components.     

Synthesis and characterization of lead phthalocyanine and its derivatives

Lead (II) phthalocyanine (PbPc); lead (II) tetranitro phthalocyanine (PbTNP) and lead (II) tetraamino phthalocyanine (PbTAP) are synthesized in pure state. These complexes are characterized using elemental analysis, UV-visible, IR-spectroscopy, X-ray crystallography and thermogravimetry. Kinetic and thermodynamic parameters associated with the thermal decomposition were calculated using thermogravimetric data. Electrical conductivity studies are done for all the three complexes using two-probe technique in the temperature range from 30 to 200 °C. The electrical conductivity observed at 30 °C are in the order PbTAP > PbTNP > PbPc. The relevant electrical conductivity data observed are reported.     

On the conductivity of an 0.01D aqueous potassium chloride solution

In a recent paper in this Journal, Saulnier and Barthel presented results for the electrolytic conductivity of 0.01 D potassium chloride solutions which they measured in a new type of conductance cell capable of absolute measurements at 0, 18 and 25°C. Their results disagreed by more than they expected from the results of Jones and Bradshaw at 18 and 25°C after they corrected the Jones and Bradshaw results to the absolute ohm and to the IPTS 1968. However their conversion was in error. The correct conversion is given and a recomparison is made with the Jones and Bradshaw results.     

Synthesis,characterization, optical,thermal and electrical properties of polybenzimidazoles

The variation of dielectric constant and dielectric loss of two novel polybenzimidazole (PBI) were studied at constant temperature with variable frequency. The polymers have shown maximum dielectric constant at low applied frequency 50 Hz at 393 K due to the space charge polarization. The AC conductivity and activation energy of polymers were arrived from dielectric constant and dielectric loss values. PBIs were synthesized by the oxidative polycondensation of benzimidazole monomers, 2-(1H-benzo [d] imidazole-2-yl)-4-bromophenol (BIBP), and 2-(1H-benzo [d] imidazole-2-yl)-6-methoxyphenol (BIMP) in an aqueous alkaline medium using NaOCl as oxidant. The monomers and polymers were characterized by various spectroscopic techniques. Fluorescence spectra of monomers and polymers showed their λ _max emission in the region of 472–479 and 463–472 nm respectively. The electrical conductivities of iodine doped polybenzimidazoles were measured by four-point probe technique and it increases with increase in iodine vapour contact time. The electrical conductivity values were correlated with the charge density on imidazole nitrogen obtained from Huckel calculation method. Both the PBI are having reasonably good thermal stability and are shown by high carbines residues of around 40% at 500°C in thermogravimetric analysis.     

Spectroscopic characterization of micro-phase separated blends of polystyrene/polymethyl methacrylate (PS/PMMA)

An investigation of the miscibility behaviour in polystyrene/ polymethyl methacrylate (PS/PMMA) blends of various compositions under different evaporations protocols using Fourier transform infrared (FT-IR) and Raman Spectroscopic techniques took place in the study. Solvent selection and evaporation rates, coupled with variations in the blend composition resulted in completely different miscibility behaviour for these systems. In particular, it was found that blends with low PMMA content result in systems that exhibit PMMA domains of less than 7 microns on average. Finally, depth profiling studies of the PMMA moiety in the PS matrix show that the distribution of the low content phase is highly affected by the solvent selection as well as the blend composition.     

Synthesis and characterization of conjugated polymers and their blends for optoelectronic applications

Various polymeric blends of hole transporting materials, (such as MEH-PPV and P3HT) and electron transporting materials (such as poly(phenyl-vinyl-quinoline) and poly[2-(4-methacryloxyphenyl)-5-phenyl)-1,3,4-oxadiazole]) have been prepared and investigated. Moreover a soluble, main chain oxadiazole bearing polyether has been synthesized, aiming towards an efficient electron transporting polymeric material which was also used for blend preparation together with P3HT. A deeper investigation into their spectroscopic characteristics using, primarily, FT-IR spectroscopy, but also UV-Vis spectroscopy has been conducted. The surface morphology of these blends was investigated using Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) in an attempt to gather information for their solid state properties and morphologies. Finally, DSC measurements provided additional insight into the thermal behaviour of these materials.     

Synthesis,characterization and corrosion inhibition in acid medium of l‐histidine Schiff base complexes

Complexes of cobalt(II), nickel(II) and copper(II) of l ‐histidine Schiff base derived from 2,4‐dihydroxybenzaldehyde and 2‐hydroxy‐1‐naphthaldehyde have been synthesized. The structures of ligands and complexes have been characterized using elemental analysis, molar conductance, magnetic moment measurements, and spectral and thermal studies. The ligands behave as tridentate, coordinating through the azomethine nitrogen and α‐hydroxyl and carboxylic oxygen atoms. The obtained results show that the Cu(II) complexes have square planar geometry, the Co(II) complexes have octahedral and tetrahedral geometries and the Ni(II) complexes have square planar and octahedral geometries. The molecular geometries of the metal complexes are supported by three‐dimensional molecular modelling using molecular mechanics (MM+) and semiempirical molecular orbital calculations (PM3). The inhibition effect of ligands and complexes on the corrosion of aluminium in 2 M H₂SO₄ was investigated using weight loss. The inhibition efficiency is found to increase with increasing inhibitor concentration and temperature. The increase in inhibition efficiency with increasing temperature is suggestive of a chemical adsorption process. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrical conductivity of hexacene doped with iodine

Hexacene (HEX) and derivatives such as dihydrohexacene and dihydroxyhexcane quinone were synthesized and thin films of them were prepared by the sublimation method. The structure and conductivity of the films both before and after doping with iodine were studied. The doped HEX film showed the conductivity of 3 × 10^?2 S/cm at room temperature, which was lower than expected since the conductivity of highly ordered pentacene was above 100 Ω^?1 cm^?1. The reason for the low conductivity was considered to be the disorder in molecular alignment since the HEX film showed an amorphous structure. A reversible change in the conductivity of the HEX film was observed in air and in vacuum.     

Synthesis and characterization of two 3-D polymeric lanthanide complexes constructed from 1,2,4,5-benzenetetracarboxylic acid

Two 3-D porous coordination polymers, [Nd(^abtec)_2/4(^bbtec)_2/4(H₂O)] _n (1) and [NdYb(^cbtec)_2/4(^dbtec)_2/4(^ebtec)_2/4(H₂O)₄] _n (2), have been prepared by the hydrothermal method at 160°C. Both complexes were characterized by elemental analyses, photoluminescence spectra, and single-crystal X-ray diffraction.     

Structural effect of polymeric acid dopants on the characteristics of doped polyaniline composites: Effect of hydrogen bonding

The conductivities of polyaniline (PANi) composites doped with the copolymeric acids such as poly(methyl methacrylate-co-p-styrenesulfonic acid) (PMMA-co-SSA), poly(styrene-co-p-styrenesulfonic acid) (PS-co-SSA), and poly(methyl methacrylate-co-2-acrylamido-2-methyl-1-propanesulfonic acid) (PMMA-co-AMPS) were investigated as a function of the acid content in the copolymeric acid dopants. With the fixed ratio of acid to aniline (1/1) in the PANi composites, the conductivities of the copolymeric acid-doped PANis decreased as the acid content in the copolymeric acids decreased. This could be attributed to the nonacidic units in the copolymeric acids which seemed to prevent adjacent acid groups from doping the PANi. Among the three kinds of copolymeric acid dopants, the PMMA-co-SSA series doped the PANi most effectively, and consequently, the PMMA-co-SSA-doped PANi composites showed the highest conductivities. The lack of conductivities of the PMMA-co-AMPS-doped PANi composites seems to be due to the doping ability of the AMPS groups. The higher conductivities of the PMMA-co-SSA-doped PANi composites rather than the PS-co-SSA-doped ones were attributed to the hydrogen bonding formed between the carbonyl groups in MMA and the amine groups in aniline which may hinder the phase separation and induce more homogeneous mixing and efficient doping. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1431–1439, 1998     

Anisotropic studies of multi-wall carbon nanotube (MWCNT)-filled natural rubber (NR) and nitrile rubber (NBR) blends

50/50 NR/NBR blends with various MWCNT loadings were prepared by mixing with MWCNT/NR masterbatches on a two-roll mill and sheeted off at the smallest nip gap. Then, the effect of milling direction, machine direction (MD) and transverse direction (TD), on the mechanical and electrical properties of the blends was elucidated. Dichroic ratio and SEM results confirmed that most of the MWCNTs were aligned along MD when MWCNT was less than 4 phr, and the number of agglomerates increased when MWCNT was more than 4 phr. Additionally, anisotropic properties were clearly observed when 4 phr MWCNT was loaded. At 4 phr MWCNT, 100% modulus and tensile strength in the MD were about 1.5 and 1.3 times higher than those in the TD, respectively. Moreover, electrical conductivity in the MD was superior to that in the TD by about 3 orders of magnitude. Results from dynamic mechanical tests also showed that the maximum tan δ in the MD sample was lower than that in the corresponding TD sample. In addition, the storage modulus at 30 °C for the MD sample containing 4 phr MWCNT was 1.15 higher than that of the corresponding TD sample. This stronger reinforcement efficiency resulted from the combination of the greater alignment and dispersion of most MWCNTs in the MD sample.