Voltammetric and waveguide spectroelectrochemical characterization of ultrathin poly(aniline)/poly(acrylic acid) films self-assembled on indium-tin oxide

We report on the spectroelectrochemical characterization of conducting polymer (CP) films, composed of alternating layers of poly(aniline) (PANI) and poly(acrylic acid) (PAA), deposited on ITO-coated, planar glass substrates using layer-by-layer self-assembly. Absorbance changes associated with voltammetrically induced redox changes in ultrathin films composed of only two bilayers (ITO/PANI/PAA/PANI/PAA) were monitored in real time using a unique multiple reflection, broadband attenuated total reflection (ATR) spectrometer. CP films in contact with pH 7 buffer undergo a single oxidation/reduction process, with ca. 12.5% of the aniline centers in the film being oxidized and reduced. The ATR spectra indicate that during an anodic sweep, the leucoemeraldine form of PANI in these films is oxidized to generate both the emeraldine and pernigraniline forms simultaneously. A comparison of the behavior observed during anodic and cathodic sweeps suggests that the rate of oxidation is limited by structural changes in the polymer film originating in electrostatic repulsion between positively charged PANI chains.     

Preparation and spectroelectrochemical characterization of composite films of poly(3,4-ethylenedioxythiophene) with 4-(pyrrole-1-yl) benzoic acid

The possibility of incorporation of 4-(pyrrole-1-yl) benzoic acid, PyBA, during electrodeposition of poly(3,4-ethylenedioxythiophene), PEDOT, is demonstrated here. The resulting novel composite material has been fabricated as moderately thin (ca 200–300 nm thick) PEDOT/PyBA film on electrode surface. As evidenced from scanning tunneling microscopy (STM) and scanning electron microscopy (SEM), morphology of the composite film is dense and granular, and it is composed of larger granules in comparison to the PyBA-free PEDOT film. It is apparent from infrared reflectance absorption spectroscopy and spectroelectrochemical measurements that the PEDOT/PyBA composite film cannot be viewed as simple mixtures of PEDOT and PyBA components. Some specific (chemical) interactions between PEDOT and PyBA can be expected. The conducting polymer serves as a robust, positively charged conductive polmer matrix for anionic (carboxylate-group derivatized) partially polymerized PyBA structures. Upon incorporation of PyBA, the overall stability of PEDOT film (resistance to dissolution during prolonged voltammetric potential cycling) has been improved. The fact, that the composite PEDOT/PyBA film is capable of preconcentrating (under open circuit conditions) both cations (Cu²⁺) or anions implies the presence of both free (available for binding) carboxylate groups and positively charged PEDOT sites. The presence of PyBA in PEDOT seems to facilitate charge propagation in the composite film. “Contribution to the International Workshop on Electrochemistry of Electroactive Materials (WEEM-2006), Repino, Russia, 24–29 June 2006”.     

Quantitative measurements of ammonium, hydrogenophosphate and Cu(II) by diffuse reflectance spectrometry

Diffuse reflectance spectrometry is shown to be useful for the quantitative determination of small amounts of pollutants. The relation between sample concentration and reflectance is described by the Kubelka-Munk equation. The experiments were performed with a laboratory constructed diode array spectrophotometer. We can obtain the quantitative reflectance values of different precipitates like ammonium with Nessler's reagent, hydrogenophosphate with silver nitrate and a complex such as Cu(II) with dithiooxamide 'rubeanic acid' by forming a spot colour on filter paper. We have obtained for each reagent a calibration curve by plotting the relative intensity of reflectance versus the log of the mol (dm(3))(-1) concentration. The linearity was obtained for Cu(II) from 8x10(-4) to 2.5x10(-2) mol l(-1) with r(2)=0.9838 and from 10(-3) to 10(-1) mol l(-1) for polyphosphate with r(2)=0.9975 and from 5x10(-4) to 5x10(-2) mol l(-1) for ammonium with r(2)=0.9889. We can consider that for a direct measurement of the intensity of reflectance, it is possible to perform quantitative spot-test analysis.     

The synthesis and characterization of monodisperse poly(acrylic acid) and poly(methacrylic acid)

A number of polyacrylic (PAA) and polymethacrylic (PMAA) acids have been synthesized by living anionic polymerization of the monomeric tert-butyl esters followed by subsequent hydrolysis of the corresponding polyesters. The necessary precautions were taken in order to assure good molecular weight control, as well as high yields in the polymerization reactions. The intermediate and final polymers were characterized by gel permeation chromatography and NMR-H¹ spectrometry.     

Activity of counterions in hydrogels based on poly(acrylic acid) and poly(methacrylic acid): Potentiometric measurements

The behavior of partially ionized weakly crosslinked gels based on poly(acrylic acid) and poly(methacrylic acid) undergoing contraction in the presence of a low-molecular-mass salt is studied experimentally. The concentration dependences of the enthalpies of swelling of gels in water and aqueous solutions with potassium chloride concentrations of 1, 10, and 100 mmol/L are determined via the method of isothermal calorimetry. On the basis of the obtained data, the enthalpy parameter of interaction between a polymer network and a medium is estimated as a function of the amount of the salt. This parameter does not exceed 0.3 and monotonically decreases with an increase in the concentration of the salt. The Donnan potential of gels depending on the concentration of KCl in the external solution is measured via the method of potentiometry with the use of capillary electrodes, and the activity of potassium counterions in the medium of hydrogel is calculated. The main factor that causes contraction of polyelectrolyte gels in a solution of a low-molecular-mass salt is a decline in the activity of counterions that leads to a decrease in the osmotic pressure inside the gel. A decline in activity may be associated with both a reduction in the activity coefficient and ionic association processes in the hydrogel.     

XPS and wettability characterization of modified poly(lactic acid) and poly(lactic/glycolic acid) films

Poly(lactic acid) (PLA) and poly(lactic/glycolic acid) copolymers (PLGA) are biodegradable drug carriers of great importance, although successful pharmaceutical application requires adjustment of the surface properties of the polymeric drug delivery system to be compatible with the biological environment. For that reason, reduction of the original hydrophobicity of the PLA or PLGA surfaces was performed by applying a hydrophilic polymer poly(ethylene oxide) (PEO) with the aim to improve biocompatibility of the original polymer. PEO-containing surfaces were prepared by incorporation of block copolymeric surfactants, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronic), into the hydrophobic surface. Films of polymer blends from PLA or PLGA (with lactic/glycolic acid ratios of 75/25 and 50/50) and from Pluronics (PE6800, PE6400, and PE6100) were obtained by the solvent casting method, applying the Pluronics at different concentrations between 1 and 9.1% w/w. Wettability was measured to monitor the change in surface hydrophobicity, while X-ray photoelectron spectroscopy (XPS) was applied to determine the composition and chemical structure of the polymer surface and its change with surface modification. Substantial reduction of surface hydrophobicity was achieved on both the PLA homopolymer and the PLGA copolymers by applying the Pluronics at various concentrations. In accordance with the wettability changes the accumulation of Pluronics in the surface layer was greatly affected by the initial hydrophobicity of the polymer, namely, by the lactide content of the copolymer. The extent of surface modification was also found to be dependent on the type of blended Pluronics. Surface activity of the modifying Pluronic component was interpreted by using the solubility parameters.     

Synthesis and characterization of poly(p-phenylene pyromellitamic acid)

Poly(p-phenylene pyromellitamic acid)s were synthesized over the weight-average molecular weight range 8,000 to 22,000. The polymers were recovered as amorphous powders composed of 3–4 × 1–2 μ platelets 0.1–0.2 μ thick containing 20–30% associated solvent. Consumption of reactants and attainment of the ultimate molecular weight of the polymer were found to occur within the first few minutes of reaction. The polymers were characterized by scanning electron microscopy; ultraviolet, visible, near-infrared, and infrared spectroscopy; x-ray analysis; viscometry; and light-scattering photometry. The intrinsic viscosity–molecular weight relation for the polymer in DMF was \documentclass{article}\pagestyle{empty}\begin{document}$ [\eta ] = 25.2 \times 10^{ - 4} \bar M_w^{0.56} $\end{document}.     

Synthesis and characterization of poly(vinylpyrrolidone-co-vinylphosphonic acid) copolymers

Radical copolymerizations of 1-vinyl-2-pyrrolidone (VP) with vinylphosphonic acid (VPA) at different feed ratios were investigated. The copolymers were characterized by ¹H-NMR, ¹³C-NMR and FT-IR. The copolymer composition was determined from the elemental analysis. Thermogravimetric analysis (TG) illustrates that the copolymers are stable up to 200 °C. Temperature dependence of the alternating current (AC) conductivities were investigated by means of impedance spectroscopy. The direct current (DC) conductivities of the samples are derived from the AC conductivity data.     

Preparation and characterization of poly(acrylic acid)-based nanoparticles

The present investigation describes the synthesis and characterization of nanoparticles based on poly(acrylic acid) (PAA) intramolecularly cross-linked with diamine, 2,2′-(ethylenedioxy)bis(ethylamine), using water-soluble carbodiimide. The aqueous colloid dispersions of nanoparticles were clear or mildly opalescent depending on the ratio of cross-linking, pH of the solution, and the molecular weight of PAA, finding consistent with values of transmittance between 3% and 99%. The structure was determined by nuclear magnetic resonance spectroscopy, and the particle size was identified by dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements. It was found that particle size depends on the pH, and at a given pH, it was caused by the ratio of cross-linking and the molecular weight of PAA. Particle size measured by TEM varied in the range of 20 and 80 nm. In the swollen state, the average size of the particles measured by DLS was in the range of 35–160 nm.     

Surface characterization of poly(L-lactic acid)-methoxy poly(ethylene glycol) diblock copolymers by static and dynamic contact angle measurements, FTIR, and ATR-FTIR

The surface composition and surface free energy properties of two types of amphiphilic and semicrystalline diblock copolymers consisting of poly(L-lactic acid) coupled to (methoxy poly(ethylene glycol) (PLLA-MePEG) having differing block lengths of PEG were investigated by using static and dynamic contact angle measurements, transmission Fourier infrared spectroscopy (FTIR), and attenuated total reflection spectroscopy (ATR-FTIR) and compared with results obtained from PLLA and MePEG homopolymers. The contact angle results were evaluated by using the van Oss-Good method (acid-base method), and it was determined that the Lewis base surface tension coefficient (gamma-) of the copolymers increased with an increase of the PEG molar content at the copolymer surface. This result is in good agreement with the transmission FTIR and ATR-FTIR results but not proportional to them, indicating that the surfaces of the copolymers are highly mobile and that the molecular rearrangement takes place upon contact with a polar liquid drop. The dynamic contact angle measurements showed that the strong acid-base interaction between the oxygen atoms in the copolymer backbone of the relatively more hydrophilic PEG segments with the Lewis acidic groups of the polar and hydrogen-bonding water molecules enabled the surface molecules to restructure (conformational change) at the contact area, so that the PEG segments moved upward, whereas the apolar methyl pendant groups of PLLA segments buried downward.     

Film characterization of poly(styrene-butylacrylate-acrylic acid)-silica nanocomposite

To improve the present unsatisfactory UV-shielding and water-resistance properties of many emulsion-type latexes, in this study, poly(styrene-butylacrylate-acrylic acid) (PSBA)-grafted-silica (PSBA-g-silica) hybrid nanoparticles were firstly prepared by suspension-dispersion-polymerization. The resulting hybrid nanoparticles were then used to add into PSBA latex to fabricate PSBA nanocomposites. The influence of PSBA-g-silica hybrid nanoparticles on the interfacial adhesion, film morphology, thermodynamics properties, UV-shielding, water-resistance and mechanical performance of PSBA films were investigated systematically. Our results revealed that filling 1.5 wt% PSBA-g-silica hybrid nanoparticles resulted in significant improvement in interfacial adhesion properties, UV-shielding, water-resistance and mechanical properties. Fabricating the silica-based latex nanocomposite is an effective approach to develop the new emulsion-type paints and adhesives.     

Crystallization measurements via ultrasonic velocity: Study of poly(lactic acid) parts

Crystallization has significant effects on the physical and mechanical properties of polymer products; therefore, crystallization measurements are important for understanding and predicting polymer products' properties. However, traditional crystallization measurement methods have disadvantages in practical applications because they can be destructive, offline, unsafe, and expensive. Recently, ultrasonic technology has shown great potential as a nondestructive, online, real‐time, and environmentally friendly measurement method for polymer characterization. In this study, a novel measurement method based on ultrasonic technology was proposed to study the crystallization characteristics of poly(lactic acid) (PLA) parts. An annealing process was employed to produce PLA parts with different degrees of crystallinity. A new ultrasonic water immersion method was used to measure the ultrasonic velocities of these annealed PLA parts. It has been found that the plot of the inverse ultrasonic velocity versus the degree of crystallinity shows good linearity over the whole crystallinity range for all three annealing temperatures. The linear relationship between the inverse of the ultrasonic velocity and the crystallinity observed in this study could provide a nondestructive method for investigating the degree of crystallinity of polymers, which can be implemented both offline and online. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 700–708     

Superabsorbent poly(acrylamide-co-itaconic acid) hydrogel microspheres: Preparation,characterization and absorbency

Poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) hydrogel microspheres were prepared via inverse suspension polymerization method. DLS results showed the formation of the monodispersed hydrogel microspheres. The size of the hydrogel microspheres could be controlled by polymerization parameters. Absorbencies of P(AM-co-IA) microspheres in water and saline were investigated and calculated by size changes of each particle before and after swelling. The results showed that P(AM-co-IA) had high absorbencies, the weight of swollen particles was above 4000 times to that of the original dried microspheres. The superabsorbent hydrogel microspheres might find the potential applications in the fields of soil amendments, water shutoff agents, and drug delivery carriers.     

Simultaneous synthesis of silver nanoparticles and poly(2,5‐dimethoxyaniline) in poly(styrene sulfonic acid)

Silver nanoparticles were formed in situ along with poly(2,5‐dimethoxyaniline) (PDMA) in an interconnected network matrix (reactor), comprising the electronic conductive polymer, PDMA, and a polyelectrolyte, poly(styrene sulfonic acid) (PSS), through the simultaneous reduction of Ag⁺ ions and polymerization of 2,5‐dimethoxyaniline. In situ ultraviolet‐visible spectroscopy showed that peaks corresponding to the plasmon resonance of silver nanoparticles at 411 nm and the polaronic transition of PDMA at 438 nm provided evidences for the simultaneous formation of silver nanoparticles and PDMA. Transmission electron microscopy and size distribution analysis revealed the presence of spherical silver nanoparticles with an average diameter of 12 nm in the composite. X‐ray photoelectron spectroscopy showed that the amine units in PDMA changed to imine units upon the formation of silver nanoparticles. A comprehensive mechanism for the formation of the PDMA‐PSS‐Ag nanocomposite is proposed. A 10‐fold increase in the conductivity was noticed for the PDMA–PSS–Ag nanocomposite (1 S/cm) in comparison with the PDMA–PSS composite (0.1 S/cm). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3843–3852, 2006     

Electrokinetic characterization of poly(acrylic acid) and poly(ethylene oxide) brushes in aqueous electrolyte solutions

Surfaces carrying hydrophilic polymer brushes were prepared from poly(styrene)-poly(acrylic acid) and poly(styrene)-poly(ethylene oxide) diblock copolymers, respectively, using a Langmuir-Blodgett technique and employing poly(styrene)-coated planar glass as substrates. The electrical properties of these surfaces in aqueous electrolyte were analyzed as a function of pH and KCl concentration using streaming potential/streaming current measurements. From these data, both the zeta potential and the surface conductivity could be obtained. The poly(acrylic acid) brushes are charged due to the dissociation of carboxylic acid groups and give theoretical surface potentials of -160 mV at full dissociation in 10(-)(3) M solutions. The surface conductivity of these brushes is enormous under these conditions, accounting for more than 93% of the total measured surface conductivity. However, the mobility of the ions within the brush was estimated from the density of the carboxylic acid groups and the surface conductivity data to be only about 14% of that of free ions. The poly(ethylene oxide) (PEO) brushes effectively screen the charge of the underlying substrate, giving a very low zeta potential except when the ionic strength is very low. From the data, a hydrodynamic layer thickness of the PEO brushes could be estimated which is in good agreement with independent experiments (neutron reflectivity) and theoretical estimates. The surface conductivity in this system was slightly lower than that of the polystyren substrate. This also indicates that no significant amount of preferentially, i.e., nonelectrostatically attracted, ions taken up in the brush.