Structure and properties of poly(vinyl alcohol)–iodine complex formed in the crystal phase of poly(vinyl alcohol) films

The structure and optical properties of the complex formed in the crystal phase of PVA that is caused by soaking at very high iodine concentration are investigated. In the resonance Raman spectra of lightly and heavily iodinated specimens, two Raman shifts appeared at 109 and 161 cm^?1. The 109 cm^?1 peak due to the I mode was much stronger than the 161 cm^?1 peak in a heavily iodinated specimen, whereas the peak was comparable with the 161 cm^?1 peak in a lightly iodinated specimen. The complex formed in the crystal phase is identified as the I mode complex. It has an averaged iodine–iodine distance of 3.2 Å, which is different from the 3.08 Å of the I mode complex formed in the amorphous phase. The effect of KI concentration in the soaking solution on the formation of the complex is also examined. The increased KI concentration in the soaking solutions at a fixed iodine concentration increases the amount of the complex formed in the crystal phase. The change in the hydrogen-bonding state in the crystal phase with the complex formation can be evidenced by IR and NMR. © 1994 John Wiley & Sons, Inc.     

Electrochemical preparation and properties of polypyrrole and its blend with poly(vinyl sulfonate) doped with perchlorate anions

In this article, we report polypyrrole (PPy)/poly(vinyl sulfonate) (PVS) and PPy/perchlorate (ClO) composite films generated by the electrochemical oxidation of pyrrole on a glassy carbon electrode (GCE) in an aqueous solution. The response of the produced films to an applied potential at 0.7 V was obtained by a cyclic voltammetry study in acetonitrile media. The films were significantly similar in their electrochemical behavior when ClO ions doped during the redox process. We concluded that with an increasing number of cycles, the anodic current increased because the number of the electroactive participants transported in the copolymer matrix was increased. Theoretical studies based on the Nernst and Butler–Volmer equations indicated that the ClO ion was transported during the oxidation/reduction process of the PPY/PVS and PPY/ClO films. The produced films were characterized further by means of IR spectroscopy, electrochemical impedance spectroscopy, and scanning electron microscopy to verify that the anion of ClO was doped into the copolymer matrix as well. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of anionic form on thermal degradation of TMAHP–cellulose

Trimethylammoniumhydroxypropyl (TMAHP)–cellulose in 10 anionic forms (F^?, Cl^?, Br^?, I^?, HSO, NO, OH^?, HCO, H₂PO, CH₃COO^?) was prepared, and the influence of each anion on thermal degradation in inert atmosphere was studied. With the help of dynamic and isothermal thermogravimetry (TG) it was found that H₂PO ions had the greatest retarding effect on TMAHP–cellulose degradation. From the values of rate constants it can be seen that all ionic forms of TMAHP–cellulose have the starting rate of thermal degradation greater than unmodified cellulose. The calculated values of activation energy of thermal degradation for different ionic forms are decreasing in following sequence: H₂PO > F^? > NO > I^? > Br^? > HCO > Cl^? > HSO > OH^? > unmodified cellulose > CH₃COO^?. From the results of pyrolyse measurements in combination with gas chromatography and mass spectrometry (Py–GC–MS) it follows that the products of the elimination of quarternary ammonium salts are trimethylamine, 3-hydroxy-2-propanone, and, in the case of OH^? form, water. In all other ionic forms the third product is the corresponding acid.     

Competitive adsorption of uranyl ions in the presence of Pb(II) and Cd(II) ions by poly(glycidyl methacrylate) microbeads carrying amidoxime groups and polarographic determination

The adsorption capacity of UO in the presence of Pb(II) and Cd(II) ions was investigated with amidoximated poly(glycidyl methacrylate) (PGMA) microbeads with an average size of 135 μm packed in a glass column (0.5‐cm i.d. and 20‐cm length, flow rate = 3 mL/min) under competitive conditions. A differential pulse polarography technique was used for the determination of trace quantities of uptaken elements by the measurement of the reduction peak currents at ?200/?950, ?400, and ?600 mV (vs a saturated calomel electrode) for UO, Pb(II), and Cd(II) ions, respectively. When only UO was found in the eluate, its adsorption was 85.3% from a 50 μM initial solution. However, when there was UO with binary systems of Pb(II) or Cd(II), it was 78.2 and 76.3%, respectively. On the other hand, in a ternary mixture of UO with Pb(II) and Cd(II), the adsorption was found to be 75.2% with the same initial concentration. According to the results, the competitive adsorption studies showed that these amidoximated PGMA microbeads had good adsorption selectivity for UO with the coexistence of Pb(II) and Cd(II) ions. The ionic strength of the solution also influenced the UO adsorption capacity of the amidoximated PGMA microbeads. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4168–4172, 2007     

Study on the thermal stability of heterogeneous nucleation effect of polypropylene nucleated by different nucleating agents

The thermal stability of the heterogeneous nucleation effect of polypropylene (PP) nucleated with an organic phosphate (A) and two kinds of sorbitol derivatives (B and D) was investigated by DSC multiscanning. For pure PP, the peak temperature of crystallization (T) was little changed with an increasing number of DSC scans, indicating that nucleation of PP is thermally stable. For the PP nucleated with an organic phosphate (PPA), the temperatures at the onset of crystallization (T) and at the completion of crystallization (T); the peak temperature of crystallization (T) and melting (T); and the heat of crystallization (ΔH_c) and fusion (ΔH_m) of PP are higher than those of pure PP and were little influenced with an increasing number of DSC scans. For PP nucleated with the sorbitol derivatives (PPB and PPD), the T, T, T, and T decreased with an increasing the number of scans. These results indicated that the thermal stability of heterogeneous nucleation effect of the nucleating agent A is higher than that of nucleating agents B and D. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1643–1650, 2002     

Several features of vinyl chloride–diallyl phthalate suspension copolymerization

Vinyl chloride–diallyl phthalate (VC–DAP) suspension copolymerization was carried out in a 5‐L autoclave and 200‐mL stainless steel vessel at 45°C. The apparent reactivity ratios of VC–DAP suspension copolymerization system were calculated as r_VC = 0.77 and r_DAP = 0.37. It shows that VC–DAP copolymer contains no gel when the feed concentration of DAP (f) is lower than a critical concentration (f_cr, inside the range of 0.466–0.493 mmol/mol VC at 80–85% conversion), the polymerization degree (DP) of copolymer increases with the increase of f and conversion. VC–DAP copolymer is composed of gel and sol fractions when f is larger than f_cr. The DP of sol fraction decreases as f increases, but the gel content and the crosslinking density of gel increase. The gel content also increases as conversion increases. The results also show that the index of polydispersity of molecular weight of sol changes with f, a maximum value appears when f is close to f_cr. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 156–162, 2000     

Intrinsic birefringence of nylon 6

Different values are reported in the literature for the intrinsic birefringence of the crystalline (Δn) and the amorphous (Δn) phases in nylon 6. Mostly, these values have either been determined by extrapolation (and then it is assumed that Δn = Δn) or calculated theoretically. In this study, intrinsic birefringence values Δn and Δn for nylon 6 were determined using the Samuels two-phase model which correlates sonic modulus with structural parameters. Three series of fiber samples were used: (1) isotropic samples of different degrees of crystallinity for estimation of E and E moduli at two temperatures. The following modulus values were obtained: 1.62 × 10⁹ and 6.66 × 10⁹ N/m² for 28.5°C, and 1.81 × 10⁹ and 6.71 × 10⁹ N/m² for ?20°C; (2) anisotropic, amorphous fiber samples for estimation of Δn = 0.076 and E = 1.63 × 10⁹ N/m² at 28.5°C; (3) semicrystalline samples of various draw ratios for estimations of Δn = 0.089 and Δn = 0.078. All measurements were carried out with carefully dried samples to avoid erroneous results caused by moisture.     

Elastic characteristics of branched-network polymers

The computed dependencies of elastic characteristics of branched-network polymers were obtained on the basis of the Takayanagi series model. The moduli ratio (λ) for branched-network and branched polymers increases as a result of an increase of the moduli ratio of network and branched phases (E/E) and the network phase fraction (V_net). The λ-increase as a function of V_net is larger than in the case of the E/E dependence. On the basis of computed dependencies, the experimental results for the radiation crosslinked SBS block copolymer were considered. The experimental results agree with the computed de-pendencies for the hetergeneous branched-network polymers with E/E ≈︁ 20. The influence of entanglements on the elastic characteristics of branched-network polymers is discussed. © 1996 John Wiley & Sons, Inc.     

Morphological studies of the modified materials: Low-density polyethylene/poly(acrylic acid)/europium(III) and low-density polyethylene/poly(acrylic acid)/uranyl ion

The morphology of low-density polyethylene (LDPE) modified by in situ sorption and thermal polymerization of acrylic acid (AA) in the matrix was examined. The microstructure of the LDPE/poly(acrylic acid) (PAA) materials after Eu³⁺ and UO ion exchange was investigated. The phase behavior of these materials was analyzed using X-ray diffraction, scanning electron microscopy (SEM), and thermal measurements (DSC). The X-ray dif-fraction studies showed that PAA is located at amorphous region of the matrix. The LDPE/PAA surface, as investigate by SEM, was apparently homogeneous before and after Eu³⁺ and UO ion exchange, respectively. Two T_g values were found for the LDPE/PAA material before and after Eu³⁺ ion exchange. Also, three and four T_g values were found for LDPE/PAA after UO ion exchange depending on the amount of UO in the modified matrix. This indicates microphase domains in the LPDE/PAA-, LPDE/PAA/Eu³⁺-, and LPDE/PAA/UO -modified materials, although a lack of visible phase separation in the micrographs was observed. © 1996 John Wiley & Sons, Inc.     

Mass transport process for the adsorption of Cr(VI) onto water‐insoluble cationic starch synthetic polymers in aqueous systems

Dynamic adsorption behaviors between Cr(VI) ion and water‐insoluble amphoteric starches was investigated. It was found that the HCrO ion predominates over the initial pH ∼ 2–4, the CrO ion predominates over the initial pH ∼ 10–12, and both ions coexist over the initial pH ∼ 6–8. The sorption process occurs in two stages: the external mass transport process occurs in the early stage and the intraparticle diffusion process occurs in the long‐term stage. The diffusion coefficient of the early stage (D₁) is larger than that of the long‐term stage (D₂) for the initial pH 4 and pH 10. The diffusion rate of HCrO ion is faster than that of CrO ion for both processes. The D₁ and D₂ values are ∼ 1.38 × 10⁻⁷–10.1 × 10⁻⁷ and ∼ 0.41 × 10⁻⁷–1.60 × 10⁻⁷ cm² s⁻¹, respectively. The ion diffusion rate in both processes is concentration dependent and decreases with increasing initial concentration. The diffusion rate of HCrO ion is more concentration dependent than that of CrO ion for the external mass transport process. In the intraparticle diffusion process, the concentration dependence of the diffusion rate of HCrO and CrO ions is about the same. The external mass transport and intraparticle diffusion processes are endothermic and exothermic, respectively, for the initial pH 4 and pH 10. The k_d values of the external mass transport and intraparticle diffusion processes are ∼ 15.20–30.45 and ∼ −3.53 to −12.67 kJ mol⁻¹, respectively. The diffusion rate of HCrO ion is more temperature dependent than that of CrO ion for both processes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2409–2418, 1999     

Electrochemical synthesis and properties of poly(3‐methylthiophene): Novel synthesis of poly(3‐methylthiophene) with pentachlorostannate and hexachloroantimonate

Poly(3‐methylthiophene) (P3‐MeT) doped with different anions were prepared electrochemically in the presence of tetraalkylammonium salts. The new poly(3‐methylthiophene) SnCl and SbCl (P3‐MeT SnCl₅ and P3‐MeT SbCl₆) were prepared electrochemically using tetra‐n‐butylammonium pentachlorostannate and tetra‐n‐butylammonium hexachloroantimonate as the supporting electrolytes. The effect of current density, salt concentration, reaction temperature, and the nature of solvents on the polymer yield and polymer conductivities have been investigated. Cyclic voltammetry of poly(3‐methylthiophene) has been examined at platinum electrode in 1,2‐dichloroethane medium containing n‐Bu₄NSnCl₅, Bu₄NSbCl₆, and Bu₄NClO₄ as the supporting electrolytes in the range of −1.0 to 1.7 V versus SCE in the presence and absence of 3‐methylthiophene. Electrical conductivity, magnetic susceptibility measurements, and structural determination by elemental analysis and infrared studies were also made. Scanning electron microscopy revealed a globular, branched, fibrous and a spongy, fibrous morphology of poly(3‐methylthiophene) SnCl, ClO, and SbCl, respectively. The thermal analysis of the polymers was also investigated. Possible causes for the observed lower conductivity of these polymers have also been discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 91–102, 1999     

Forced oscillations in continuous flow stirred tank reactors with nonlinear step growth polymerization

The self-step growth polymerization of RA_f monomers in homogeneous, continuous flow stirred tank reactors (HCSTRs) is simulated under conditions of periodic feed concentration (with frequency ω and amplitude α). By having periodic operation, the polydispersity index of the polymer is found to increase by about 35% over the values at steady state. Periodic operation of HCSTRs is found to lead to gelation only for certain values of the frequency and the dimensionless residence time τ^*. Gelling envelopes have been obtained to give conditions under which HCSTRs should be operated. These envelopes can be described in terms of two critical dimensionless residence times, τ and τ such that nongelling operation is always ensured when τ^* < τ. For τ^* > τ, periodic operation always leads to gelation, and HCSTRs cannot be used. For τ < τ^* < τ, the gelling behavior is found to depend on the functionality f, amplitude α, and the dimensionless residence time τ^*.     

The effect of side chains on the partial specific volumes of poly(o-alkylphenyl methacrylate)s and polydiitaconates

Partial specific volumes ν of a series of poly(o-alkyl phenyl methacrylate)s and polydiitaconates were determined by density measurements, in toluene and tetrahydrofuran solutions, respectively. The effect of the size and nature of the side groups on partial specific volume is analyzed. Good agreement is found between the experimental ν values and those obtained theoretically from the group contribution method.     

Melting behavior of poly(trimethylene terephthalate)

In this study, the melting behavior of isothermally crystallized polytri‐ methylene terephthalate (PTT) was investigated. Multiple melting behaviors in DSC heating trace were found because two populations of lamellar stacks were formed during primary crystallization and the recrystallization at heating process, respectively. This fact could be also confirmed from the result of optical microscopy observation. The Hoffman–Weeks equation was applied to obtain equilibrium melting temperature (T). The T value of PTT is about 525 K, which is 10 K higher than that reported. Combining the enthalpy of fusion from the DSC result and the degree of crystallinity from WAXD result, the value of the equilibrium‐melting enthalpy ΔH was deduced to be approximately 28.8 kJ mol^?1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2426–2433, 2002     

Surface free energy analysis of polymers and its relation to surface composition

The dispersion force component of surface free energy, γ, and the nondispersive interaction free energy between solid and water, I, were determined by the two-liquid contact-angle method, i.e., by the measurement of contact angles of water drops on plain solids in hydrocarbon, for commercialy available organic polymers such as nylons, halogenated vinyl polymers, polyesters, etc. A method to estimate the I values from the knowledge of the polymer composition is also proposed, on the basis of the assumption of the spherical monomer unit and the sum of interactions between functional groups and water molecules at the surface.     

Kinetics of methyl methacrylate grafting polymerization onto flaky aluminum powder

With ammonium persulfate (APS) as the initiator, the kinetics of methyl methacrylate (MMA) grafting polymerization onto flaky aluminum powder (Al) was studied. It was found that the experimental apparent grafting polymerization rate, R_g = KC × C × C, was basically consistent with the theoretical result based on the theory of stable polymerization and equivalent activity, R_g = KC × C × C_MMA. The activation energy of grafting, homogenous, and total polymerization rate was calculated as 65.1, 35.4, and 37.5 kJ mol^?1, respectively. It could be validated that the relationship among these activation energies accorded with the theoretical result of parallel reactions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Use of amidoximated acrylonitrile/N‐vinyl 2‐pyrrolidone interpenetrating polymer networks for uranyl ion adsorption from aqueous systems

Poly(N‐vinyl 2‐pyrrolidone) (PVP)/acrylonitrile (AN) interpenetrating polymer networks (IPNs) were synthesized and amidoximated for the purpose of uranyl ion adsorption. The adsorption of amidoximated IPNs was studied from different uranyl ion solutions (850, 1000, 1200, 1400, and 1600 ppm). The result of all our adsorption studies showed that the bonding between UO‐amidoxime groups complied with the Langmuir‐type isotherm. The adsorption capacity was found as 0.75 g UO/g dry amidoximated IPN. In order to increase the UO ion adsorption capacity the amidoximated IPN was treated with alkali, but no significant increase could be observed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2324–2329, 2001     

Synthesis and electrochemistry of grafted copolymers of cellulose with 4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone,and 9-vinylcarbazole

Some new cellulosic materials, suitable for the adsorption of noble metal ions, were syn-thesized by chemical and electrochemical modification of cellulose. The polymerizable groups were introduced in cellulose with ∼ 80% yield of substitution by esterification with acryloyl chloride. The vinyl monomers (4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone, and 9-vinylcarbazole) were readily grafted into cellulose acrylate via radical polymerization in acetonitrile. The grafted copolymers of cellulose with 4-vinylpyridine and 4-vinylimidazole were reacted with methyl iodide and the corresponding 1-methylpyridinium iodide ( 6 ) and 3-methylimidazolium iodide ( 7 ) copolymers of cellulose were obtained. Copolymers 6 and 7 were transformed into new polymeric regents, differing in anions (ClO, CF₃COO⁻, NO, p-TsO⁻, BF, PF) by using a supporting electrolyte carrying the desired anions through the ion-exchange-electrochemical oxidation of the released iodide at a controlled anodic potential. © 1996 John Wiley & Sons, Inc.     

Gas permeabilities of poly(trimethylsilylpropyne) membranes surface modified with CF4 plasma

Surface fluorination of poly(trimethylsilylpropyne) (PTMSP) membranes by CF₄ plasma was studied. The surface fluorination of the membranes was carried out in an atmosphere of CF₄ in a capacitively coupled discharge apparatus with external electrodes. Dramatic increase in selectivity (P/P) was observed. The effect of fluorination conditions such as duration of treatment and discharge power on the permeabilities of the membranes was studied. X-ray photoelectron spectrometric data of modified PTMSP membranes showed a drastic alternation in the surface layer. The P and P/P of the membranes were observed to be dependent on the F/C atomic ratio. At F/C > 1, the P/P value of the membranes could be more than four. © 1993 John Wiley & Sons, Inc.     

The influence of the equilibrium melting temperature on the supermolecular morphology of several polymers

At a constant isothermal crystallization temperature (T_c), the crystalline morphologies of several polymers have been found to be a function of the melt-liquid temperature (T₁). At a constant T_c below a critical crystallization temperature (T [about 0.9 T(K)], a transition from a nonspherulitic to a spherulitic morphology occurs when the melt liquid is heated above a melt-liquid transition temperature, (T_lt) [approximately 1.03 T_m (K)], where T_m is the observed melting temperature of the sample. The melt-liquid transition temperature, T_lt, which experimentally affects the visible morphology of a semicrystalline polymer, is apparently indistinguishable from the thermodynamic melting temperature, T, determined by the Hoffman-Weeks procedure. The X-ray powder diffraction patterns of spherulitic and nonspherulitic morphologies were identical, independent of the heating-cooling cycle. This suggests that the transition that occurs at T_It does not affect the arrangement of polymer molecules in the crystallite, but only the manner in which the crystallites are arranged in the supermolecular morphology. The evidence suggests, at least for the polymers studied, that a residual order exists in the melt until the T or T_It of the particular polymer is reached. © 1993 John Wiley & Sons, Inc.