Adsorption characterization of lead(II) and cadmium(II) on crosslinked carboxymethyl starch

The adsorption of Pb(II) and Cd(II) ions with crosslinked carboxymethyl starch (CCS) was investigated as function of the solution pH, contact time, initial metal‐ion concentration, and temperature. Isotherm studies revealed that the adsorption of metal ions onto CCS better followed the Langmuir isotherm and the Dubinin–Radushkevich isotherm with adsorption maximum capacities of about 80.0 and 47.0 mg/g for Pb(II) and Cd(II) ions, respectively. The mean free energies of adsorption were found to be between 8 and 16 kJ/mol for Pb(II) and Cd(II) ions; this suggested that the adsorption of Pb(II) and Cd(II) ions onto CCS occurred with an ion‐exchange process. For two‐target heavy‐metal ion adsorption, a pseudo‐second‐order model and intraparticle diffusion seem significant in the rate‐controlling step, but the pseudo‐second‐order chemical reaction kinetics provide the best correlation for the experimental data. The enthalpy change for the process was found to be exothermic, and the ΔS^θ values were calculated to be negative for the adsorption of Pb(II) and Cd(II) ions onto CCS. Negative free enthalpy change values indicated that the adsorption process was feasible. The studies of the kinetics, isotherm, and thermodynamics indicated that the adsorption of CCS was more effective for Pb(II) ions than for Cd(II) ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Moisture sorption/desorption behavior of various manmade cellulosic fibers

The kinetics of dynamic water vapor sorption and desorption on viscose, modal, cotton, wool, down, and polyester fibers and lyocell knit fabrics were investigated according to the parallel exponential kinetics (PEK) model. The total equilibrium moisture regain (M_inf(total)) in all the materials decreased with increasing temperature. However, the partial equilibrium fast sorption, determined by PEK simulation at 60% relative humidity (RH) and 36°C, was larger than that at 20°C, whereas the partial equilibrium slow sorption was smaller. The characteristic times in fast sorption (τ₁) and in slow sorption (τ₂) for lyocell were reduced when the conditions were changed from 60% RH and 20°C to 36°C, whereas those for the other fibers increased. Lyocell exhibited the highest M_inf(total) value and the lowest τ₁ and τ₂ values, and this suggested high equilibrium moisture content and fast moisture uptake/release, that is, high moisture accessibility for lyocell. The relationships between the moisture regain, hysteresis, water retention capacity, and Brunauer–Emmett–Teller surface volume in the materials were also examined. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1621–1625, 2005     

Study on propene polymerization using a novel spherical Ziegler‐Natta catalyst and its kinetics

The effects of the Al/Ti ratio and external donor (ED) on the catalytic activity and kinetics of propene polymerization catalyzed by a spherical Ziegler‐Natta (Z‐N) catalyst were investigated. The preparation conditions of the catalyst play an important role in the polymerization kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3737–3740, 2003     

Graft copolymerization of an itaconic acid/acrylamide monomer mixture onto poly(ethylene terephthalate) fibers with benzoyl peroxide

A mixture of acrylamide (AAm) and itaconic acid (IA) was grafted onto poly(ethylene terephthalate) (PET) fibers with benzoyl peroxide in aqueous media. The effects of polymerization conditions such as the temperature, polymerization time, initiator concentration, and monomer mixture ratio on grafting were investigated. The maximum graft yield was 76.1% with an AAm/IA mixture ratio of 90/10 (mol/mol). The graft yield was as low as 3% in the single grafting of IA, whereas the use of AAm as a comonomer increased the amount of IA that entered the fiber structure to 33.5%. An increase in the temperature from 65 to 85°C increased the grafting rate and saturation graft yield. However, an increase in the temperature above 85°C decreased the saturation graft yield. The graft yield increased up to an initiator concentration of 1.0 × 10^?2 M and decreased afterwards. The grafting rate was 0.65th‐ and 0.74th‐order with respect to the initiator and AAm concentrations, respectively. The densities, diameters, and moisture‐regain values of the AAm/IA‐grafted PET fibers increased with the graft yield. Similarly, there was an increase in the dyeability of the AAm/IA‐grafted fibers with acidic and basic dyes. The grafted fibers were characterized with Fourier transform infrared and thermogravimetric analysis, and their morphologies were examined with scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1795–1803, 2005     

Thermal degradation kinetics of polyesters containing mesogenic aromatic diols

A series of polyesters were synthesized by reacting structurally differing aromatic diols with either saturated (flexible) or unsaturated (rigid) dicarboxylic acid halide by a stirred interfacial polycondensation technique. Thermal degradation kinetics of these polyesters were investigated by applying Coats–Redfern and Horowitz–Metzger nonisothermal procedures. The dynamic thermogravimetry experiments were conducted in nitrogen to obtain differential thermogravimetric plots. Thermal stability of these polyesters was discussed on the basis of semiquantitative methods such as differential procedural decomposition temperature, integral procedural decomposition temperature, and fraction decomposition temperature (e.g., 10% DT). Degradation proceeded in multiple stages. The thermal degradation patterns and activation energies in these stages were discussed in relation to central bridging moieties of aromatic diol. The activation energies of these polyesters were found to be in the range of 100 to 200 kJ/mol. The effect of spacer type on activation energy was also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 784–792, 2005     

Adsorption behavior of monomers and formation of conducting polymers on polyester fibers

In situ adsorption of monomers on fibers plays a key role in fabricating highly conductive polyaniline (PANI)‐based textiles by two‐stage oxidation polymerization. Experiments were conducted in aniline monomer and hydrochloric acid solution with the variables such as contact time, initial concentration, and temperature, which can enhance the equilibrium adsorption capacity to aniline of poly(ethylene terephthalate) (PET) fibers. Equilibrium data were fit well by a Henry partition‐type isotherm equation. It was found that the kinetics of the adsorption of aniline onto PET fibers at different operating conditions was best described by the pseudo‐second‐order model. The rate parameters of the intraparticle diffusion model for adsorption were also evaluated and compared to identify the adsorption mechanisms. The monomer exhaustion increased with increasing the temperature. The value of electrical surface resistance of conductive textiles about 3.2 kΩ was obtained when the padder squeeze step was introduced, and the molar ratio of 0.6 between the oxidant concentration and the exhausted concentration of monomers at the adsorption equilibrium was applied. Scanning electron micrographs of PANI/PET composite surfaces were observed, conforming that smooth films were produced by surface polymerization of aniline monomers adsorbed previously on fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Isothermal crystallization kinetics of anhydrous sodium acetate nucleated poly(ethylene terephthalate)

Studies on the isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nucleated with anhydrous sodium acetate were carried out. The nucleated agent had succeeded in promoting greater rates of crystallization in PET. A study of the melting behavior of the samples revealed that the nucleating agents promoted formation of thinner lamellae. The equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman Weeks procedure. The nonlinear Hoffman Week's procedure was found to be inapplicable in the current study. The Lauritzen‐Hoffman secondary nucleation theory was applied to determine the nucleation parameter (K_g), fold surface energy (σ_e), and work of chain folding (q). σ_e and q decreased on addition of nucleating agent. The approximate and exact form of the Lauritzen Z‐test was used to determine the operating regime. The operating regime was found to be primarily regime II for the range of temperatures studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fluorescence method using labeled chromophores to study the curing kinetics of a polyurethane system

A fluorescence method using labeled chromophores to study the curing kinetics of a polyurethane (PU) system was developed. A PU system based on fluorescent‐labeled hexamethylene diisocyanate and a polyol (polyether/polyester) was cured at different temperatures (25, 40, 50, and 65°C). The fluorescent response from the 5‐dimethylaminonaphtalene‐1‐(N‐2‐aminoethyl)sulfonamide and 4‐methacryloylamino‐4′‐nitrostilbene moieties chemically bonded to the PU system was monitored as a function of the curing time. With the fluorescence data, it was possible to model the kinetics of the curing process. Methods based on the fluorescence intensity ratio and the first moment of the fluorescent band emission were applied to determine the degree of curing of the PU system. In addition, it was possible to calculate an apparent activation energy for the curing process, and a value of 17 kJ/mol was obtained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2992–3000, 2002     

Nonisothermal crystallization kinetics of poly(butylene terephthalate)/montmorillonite nanocomposites

The melt intercalation method was employed to prepare poly(butylene terephthalate) (PBT)/montmorillonite (MMT) nanocomposites, and the microstructures were characterized with X‐ray diffraction and transmission electron microscopy. Then, the nonisothermal crystallization behavior of the nanocomposites was studied with differential scanning calorimetry (DSC). The DSC results showed that the exothermic peaks for the nanocomposites distinctly shifted to lower temperatures at various cooling rates in comparison with that for pure PBT, and with increasing MMT content, the peak crystallization temperature of the PBT/MMT hybrids declined gradually. The nonisothermal crystallization kinetics were analyzed by the Avrami, Jeziorny, Ozawa, and Mo methods on the basis of the DSC data. The results revealed that very small amounts of clay (1 wt %) could accelerate the crystallization process, whereas higher clay loadings reduced the rate of crystallization. In addition, the activation energy for the transport of the macromolecular segments to the growing surface was determined by the Kissinger method. The results clearly indicated that the hybrids with small amounts of clay presented lower activation energy than PBT, whereas those with higher clay loadings showed higher activation energy. The MMT content and the crystallization conditions as well as the nature of the matrix itself affected the crystallization behavior of the hybrids. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3257–3265, 2006     

Preparation,curing kinetics,and thermal properties of bisphenol fluorene epoxy resin

Diglycidyl ether of 9,9‐bis(4‐hydroxyphenyl) fluorene (DGEBF) was synthesized to introduce more aromatic structures into an epoxy resin system. The structure of DGEBF was characterized with Fourier transform infrared and ¹H‐NMR. 4,4′‐Diaminodiphenylmethane (DDM) was used as the curing agent for DGEBF, and differential scanning calorimetry was applied to study the curing kinetics. The glass‐transition temperature of the cured DGEBF/DDM, determined by dynamic mechanical analysis, was 260°C, which was about 100°C higher than that of widely used diglycidyl ether of bisphenol A (DGEBA). Thermogravimetric analysis was used to study the thermal degradation behavior of the cured DGEBF/DDM system: its onset degradation temperature was 370°C, and at 700°C, its char yield was about 27%, whereas that of cured DGEBA/DDM was only 14%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Solid‐state polymerization of poly(ethylene 2,6‐naphthalate)

The solid‐state polymerization (SSP) of poly (ethylene 2,6‐naphthalate) (PEN) was studied and compared with that of poly(ethylene terephthalate) (PET). The SSP of PEN, like that of PET, could be satisfactorily described with a modified second‐order kinetic model, which was based on the assumptions that part of the end groups were inactive during SSP and that the overall SSP followed second‐order kinetics with respect to the active end‐group concentration. The proposed rate equation fit the data of the SSP of PEN quite well under various conditions. PEN prepolymers in pellet and cube forms with intrinsic viscosities (IVs) ranging from 0.375 to 0.515 dL/g, various particle sizes, and various carboxyl concentrations were solid‐state polymerized at temperatures ranging from 240 to 260°C to study the effects of various factors. The SSP data obtained in this study could be readily applied to the design of commercial PEN SSP processes. Because PEN and PET share the same SSP mechanism, in general, the SSP behaviors of PEN are similar to those of PET. Thus, the SSP rate of PEN increased with increasing temperature, increasing prepolymer IV, and decreasing prepolymer particle size. However, because of the much higher barrier properties of PEN, the prepolymer particle size and carboxyl concentration had much greater effects on the SSP of PEN than on the SSP of PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1075–1084, 2007     

Studies of the curing kinetics and thermal stability of epoxy resins using a mixture of amines and anhydrides

This article describes the curing and thermal behavior of diglycidyl ether of bisphenol A with phthalic anhydride (PA)/pyromellitic anhydride/diaminodiphenyl sulfone (DDS) or a mixture of anhydrides and amines in varying ratios as curing agents. The kinetics of the curing behavior was investigated with a multiple‐rate method. The activation energy of the curing reaction as determined in accordance with Ozawa's method was found dependent on the structure of the anhydride and on the ratio of amines to anhydrides. The activation energy was highest with sample DP3 (0.25 : 0.75) and DM3 (0.25 : 0.75). We evaluated the thermal stability of epoxy resin, cured isothermally, by recording thermogravimetric traces in a nitrogen atmosphere. The char yield was highest for resins cured with a mixture of DDS and PA (0.5 : 0.5) and a mixture of DDS and pyromellitic dianhydride (0.25 : 0.75). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3919–3925, 2006     

Kinetics of the curing reaction of unsaturated polyester resins catalyzed with new initiators and a promoter

In this article, the curing of unsaturated polyester resins catalyzed with a promoter [cobalt(II) octoate] and free‐radical initiators is presented. The new initiators were formed by the oxidation process of ethyl methyl ketone or cyclohexanone with hydrogen peroxide and the mixture of solvents containing hydroxyl groups. As a reference, a typical curing system containing ethyl methyl ketone hydroperoxide (Luperox) and the promoter was used. The differential scanning calorimetry runs were performed at different heating rates. The experimental data were fitted with the empirical kinetic model. First, the kinetic parameters (activation energy, frequency factor, and reaction order) were obtained with a single reactive process and with the nth‐order reaction f(α), the nth‐order reaction f(α) with autocatalysis, and the first‐order reaction f(α) with autocatalysis. Second, two or three different reactive processes with the nth‐order reaction f(α) for each step were used. The obtained values of the activation energies for the curing of the unsaturated polyester resins with the free radical initiator–cobalt(II) salt catalytic system were in the range 40–60 kJ/mol for the polymerization initiated by the redox decomposition of the initiators and 80–90 kJ/mol for the polymerization initiated by the thermal decomposition of the initiators at high temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1870–1876, 2006     

Microemulsion polymerization kinetics and mechanisms

The mechanisms of microemulsion polymerizations stabilized by sodium dodecyl sulfate in combination with pentanol were investigated with a water‐insoluble dye as the probe. The major parameters chosen for study were the types of initiators [water‐soluble sodium persulfate (SPS) vs oil‐soluble 2,2′‐azobisisobutyronitrile (AIBN)] and the polarity of the monomers [relatively hydrophobic styrene (ST) vs relatively hydrophilic methyl methacrylate (MMA)]. Both continuous particle nucleation and limited particle flocculation had a significant influence on the polymerization kinetics. For the polymerizations investigated in this work, the relatively low initiation efficiency of AIBN resulted in a reaction system showing a quite different particle nucleation mechanism than that of the ST polymerization with SPS. The formation of particle nuclei in water was suppressed to some extent, and microemulsion droplet nucleation predominated in the ST polymerization initiated by AIBN. Homogeneous nucleation played an important role, and a mixed mode of particle nucleation (microemulsion droplet nucleation and homogeneous nucleation) was operative in the MMA polymerization. The MMA polymerization experienced stronger particle flocculation than its ST counterpart. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2005–2013, 2005     

Kinetic and Thermodynamic Studies of Emulsion Polymerization of a Sugar Monomer by Calorimetry with Compensation Heating and Differential Cooling

The kinetic and thermodynamic features of free‐radical batch emulsion polymerization of a sugar monomer (3‐MDG) and butyl acrylate (BA) were investigated in a power compensation calorimeter. The homopolymerizations as well as the copolymerization have been studied. The overall activation energy of 3‐MDG homopolymerization was 140 ± 3.8 kJ · mol^?1, the polymerization enthalpy was ΔH_MDG = ?51.6 ± 1.9 kJ · mol^?1 and the calculated adiabatic temperature rise was ΔT_ad = 78.5 K. The effects of the initiator and the emulsifier concentrations on the 3‐MDG/BA batch copolymerization kinetics and on the colloidal properties of the final sugar latexes were studied at 60 °C. At higher emulsifier and initiator concentration, respectively, the polymerization rate increases and the particle size decreases, but the trends do not conform to the Smith‐Ewart theory. Polydisperse sugar latex particles with a mean diameter in the range of 50–67 nm were obtained.

Relationship between the activation energy and the conversion for BA (open symbols) and 3‐MDG (solid symbols).     

Adsorption characteristics of benzene on electrospun‐derived porous carbon nanofibers

The adsorption properties of polyacrylonitrile (PAN) carbon nanofibers fabricated by using an electrospinning route were assessed for their applicability as a novel alternative adsorbent. Commercial fiber, A–10, was chosen for comparison. Nitrogen adsorption/desorption isotherms and gravimetric techniques were used to examine the porous structure, adsorption equilibrium, kinetics, and the energetic heterogeneity of the prepared adsorbent. The nitrogen adsorption and desorption isotherms showed that PAN carbon nanofibers are highly microporous with small amounts of mesoporous regions. The equilibrium data of benzene was obtained at three different temperatures (343.15, 383.15, and 423.15) K with pressures up to 4 kPa. The data correlated successfully with the Toth isotherm equation. In addition, by using this isotherm model, the adsorption affinity and isosteric enthalpy of adsorption were determined. The results of the isosteric enthalpy of adsorption and adsorption energy distribution tests/equations revealed that although PAN carbon nanofibers have a heterogeneous surface, they seem to be more homogeneous than commercial carbon fibers. Moreover, the mass transfer and thermal desorption results showed that shallow pores contained within PAN carbon nanofibers may be effective adsorbents for removing toxic compounds. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2454–2462, 2006     

Removal of Cu(II) by polypyrrole deposits on stainless steel mesh

The reduction of Cu(II) in aqueous media by polypyrrole deposits on stainless steel mesh is examined in this work. The kinetics of Cu(II) reduction, the influence of temperature, and the possibility of the regeneration and reuse of polypyrrole for Cu(II) reduction have been investigated. The morphology of stainless steel mesh/polypyrrole electrodes has been monitored with scanning electron microscopy. The X‐ray diffraction technique has been used to detect the formation of metallic copper deposits on the surface of polypyrrole films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 629–633, 2007     

Structure and reaction mechanism for the monoacid diol polyester from caprolactone and 2,2′‐bis(hydroxymethyl)propionic acid: NMR and melting‐point evidence

The product distribution in the synthesis of acidic hydroxypolyesters from a 6/1 mol ratio of caprolactone and 2,2′‐bis(hydroxymethyl)propionic acid (DMPA) changes with reaction time and temperature. ¹³C‐nuclear magnetic resonance (NMR) signals were identified that are specific for all the possible substitution products around the quaternary carbon in the DMPA. This allows quantitative determination of the six different species that are present. NMR studies showed that over one‐half of the product is substituted on only one of the DMPA hydroxyls. The residual DMPA concentration increases at times and temperatures higher than those required to just complete caprolactone conversion because of equilibration of the kinetic product. All process conditions produced polyesters with two melting points. This suggests that the monosubstituted and disubstituted families of oligomers which are present are not completely miscible with one another. Polyester melting points increase as reaction time and temperature increase. This indicates that the degree of polymerization of the polycaprolactone arms increases as the severity of the preparative condition increases. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2217–2226, 2001     

Study on curing kinetics and curing mechanism of epoxy resin based on diglycidyl ether of bisphenol a and melamine phosphate

The curing kinetics of the diglycidyl ether of bisphenol A/melamine phosphate (DGEBA/MP) was analyzed by the DSC technique. The Kissinger and Flynn–Wall–Ozawa methods were applied to determine the dynamic kinetics of the DGEBA/MP system. The activation energies obtained by these two methods were 83.9 and 85.6 kJ/mol, respectively. An autocatalytic equation was applied to determine the isothermal curing kinetics of the DGEBA/MP system. The DGEBA/MP system exhibits autocatalytic behavior in the isothermal curing procedure, whose kinetics fits well with the autocatalytic mechanism. The obtained isothermal curing activation energy of the DGEBA/MP system was 110.0 kJ/mol. The curing mechanism of DGEBA with melamine phosphate was investigated using FTIR, ¹³C solid‐state NMR, and ³¹P solid‐state NMR. It involved an epoxide–amine reaction, etherification of phosphoric acid and epoxy, dehydration, and thermal oxidation of the hydroxyl group of the DGEBA/MP system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 892–900, 2004     

Concentrated emulsion polymerization of methyl methacrylate/butyl acrylate initiated by a redox system

Stable concentrated emulsions of methyl methacrylate/butyl acrylate were prepared with sodium dodecyl sulfate and cetyl alcohol as the compound surfactant and poly(vinyl alcohol) as the major reinforcer of the liquid film. With a redox system based on benzoyl peroxide/N,N′‐dimethyl phenylamine introduced into the concentrated emulsions, polymer particles with different shapes and sizes were obtained by initiation of the polymerization at low temperatures. We investigated the kinetic behaviors of concentrated emulsion polymerization and drew linear regression diagrams of its time–conversion curves in a constant rate phase (conversions ranged from 20 to 70%), and the experimental results show that the variation of the concentrations of the compound surfactant and initiator, the categories of reinforcers of the liquid film, the temperatures, and so on were responsible for the polymerization stability and the polymerization rate. Finally, the kinetics equation and activation energy of the initiator were obtained. The particle size and distribution of particle diameters of latex particles were determined by photon correlation spectroscopy. The determination results reveal that concentrations of the compound surfactant, polymerization temperatures, and so on affected the shape and size of the polymer particles greatly. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1695–1701, 2005