Poly(acrylamide‐co‐maleic acid) hydrogels for removal of Cr(VI) from aqueous solutions,Part 1: Synthesis and swelling characterization

The swelling behavior of poly (acrylamide‐co‐maleic acid) hydrogels has been investigated in distilled water at 30°C. The gels were characterized with respect to structural parameters, Fourier transform infrared, and thermogravimetric analysis. The gels showed fair pH‐dependent swelling and exhibited double “s”‐shaped curve between equilibrium water uptake and pH of the swelling media. The two pK_a values, as determined from the curve, were found to be 2.46 and 6.58. The activation energy of the water uptake process for plain and acid containing gels was found to be 7.93 and 3.26 kJ mol^?1 respectively. Similarly, the enthalpy of mixing between dry polymer and solvent showed positive values, thus indicting endothermic nature of the process, and the values increased from 10.06 to 16.29 kJ mol^?1 with increase in acid content from 2.1 × 10^?1 to 4.7 × 10^?1 mM respectively. There was an optimum initiator concentration 24.0 × 10^?2 mM and reaction temperature 60°C at which gels synthesized showed maximum absorbency. The dilution of the reaction mixture resulted in the formation of hydrogels with enhanced absorbency. Finally, the gels with varying content of monomer acid in the feed mixture showed different swelling behavior when studied in the medium of pH 1.0 and 7.0. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2759–2769, 2006     

Fluorescence Quenching in Three to Zero Dimensions: Effect of Dimensionality on a Diffusion-Limited Reaction

The diffusion-limited fluorescence quenching of pyrene by a hydrophobic benzophenone derivative, 1-(4-benzoyl)-phenylhexane, was investigated in the different phases of the binary system hexaethyleneglycol-mono-n-dodecylether (C₁₂E₆)-water, from the normal homogeneous solution of the neat surfactant, via a sequence of liquid crystalline phases, to the aqueous micellar solution. These phases provide nonpolar domains of various dimensionality for the reactants: three dimensions in the neat surfactant, two in the lamellar phase, one in the hexagonal phase, and zero in the small micelles. The results were evaluated using models with appropriate dimension for the diffusion-controlled reaction. The resulting diffusion coefficients at 20°C were obtained as 3 × 10⁻¹¹ m² s⁻¹ in the neat surfactant, around 6 × 10⁻¹¹ m² s⁻¹ in the lamellar phase, and 10 × 10⁻¹¹ m² s⁻¹ in the hexagonal phase. The activation energy for the diffusion process increased from 32 kJ mol⁻¹ in the neat surfactant to 42 kJ mol⁻¹ in the hexagonal phase. The differences between the phases may be due to the uncertainty in the values of the size parameters for the structures; in any case, they are not large, indicating that it is mainly the geometry that is important for the deactivation kinetics, whereas the mobilities of the reactants are less affected by changes in packing.     

Preparation and drug‐release behavior of minocycline‐loaded poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] films

In this work, biocompatible hydrogel matrices for wound‐dressing materials and controlled drug‐release systems were prepared from poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] [p(HEMA‐co‐PEG–MA] films via UV‐initiated photopolymerization. The characterization of the hydrogels was conducted with swelling experiments, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis (differential scanning calorimetry), and contact‐angle studies. The water absorbency of the hydrogel films significantly changed with the change of the medium pH from 4.0 to 7.4. The thermal stability of the copolymer was lowered by an increase in the ratio of poly(ethylene glycol) (PEG) to methacrylate (MA) in the film structure. Contact‐angle measurements on the surface of the p(HEMA‐co‐PEG–MA) films demonstrated that the copolymer gave rise to a significant hydrophilic surface in comparison with the homopolymer of 2‐hydroxyethyl methacrylate (HEMA). The blood protein adsorption was significantly reduced on the surface of the copolymer hydrogels in comparison with the control homopolymer of HEMA. Model antibiotic (i.e., minocycline) release experiments were performed in physiological buffer saline solutions with a continuous flow release system. The amount of minocycline release was shown to be dependent on the HEMA/PEG–MA ratio. The hydrogels have good antifouling properties and therefore are suitable candidates for wound dressing and other tissue engineering applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics of combined noncatalytic and catalytic hydrolysis of jute fiber under ultrasonic–far infrared energy synergy

Hydrolysis of pretreated waste jute fiber was intensified for maximizing reducing sugar (RS) yield deploying a novel reactor equipped with ultrasonic–far-infrared-waves (US–FIRW). At optimal 70°C temperature, 2.5 wt% Amberlyst-15 catalyst concentration, 15 min hydrolysis time and 10 (wt/wt) water loading; US–FIRW rendered significantly greater RS yield (74.82 mol%) compared to other reactors provided with far-infrared-wave (69.63 mol%), ultrasonication (50.34 mol%), and conventional thermal system (48.16 mol%). Kinetic models were developed considering noncatalytic-pseudo-homogenous (NCPH) in addition to the combined catalytic-pseudo-homogeneous (CPH) and catalytic heterogeneous (CHE) hydrolysis pathways. The results revealed that pseudo-homogenous–heterogeneous Eley–Rideal (PHHER) model could represent the hydrolysis kinetics most accurately. Remarkably, the lowest activation energy [16.75 kJ mol⁻¹ (NCPH), 13.82 kJ mol⁻¹ (CPH), 40.01 kJ mol⁻¹ (CHE)] required in US–FIRW evidently established its greater energy-efficiency among investigated reactors. The novel reactor and the simulated kinetic models can be applicable to other lignocellulosic biomass conversion for sustainable biorefinery.     

Characterization and determination of swelling and diffusion characteristics of poly(n‐vinyl‐2‐pyrrolidone) hydrogels in water

Hydrogels in the form of rods with varying crosslink densities and three‐dimensional network structures were prepared from Poly(N‐vinyl‐2‐pyrrolidone) (PVP)/water and PVP/water/persulfate systems by irradiation with γ rays at ambient temperature. Average molecular weights between crosslinks, percent swelling, swelling equilibrium values, diffusion/swelling characteristics (i.e., the structure of network constant, the type of diffusion, the initial swelling rate, swelling rate constant), and equilibrium water content were evaluated for both hydrogel systems. Water diffusion to the hydrogel is a non‐Fickian type diffusion and diffusion coefficients vary from 6.56 × 10⁻⁷ to 2.51 × 10⁻⁷cm²min⁻¹ for PVP and 6.09 × 10⁻⁷ to 2.14 × 10⁻⁷ cm²min⁻¹ for PVP/persulfate hydrogel systems. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 994–1000, 2000     

Colon‐specific oral delivery of vitamin B2 from poly(acrylamide‐co‐maleic acid) hydrogels: An in vitro study

Hydrogels, composed of poly(acrylamide‐co‐maleic acid) were synthesized and the release of vitamin B₂ from these gels was studied as a function of the pH of the external media, the initial amount of the drug loaded, and the crosslinking ratio in the polymer matrix. The gels containing 3.8 mg of the drug per gram gel exhibit almost zero‐order release behavior in the external media of pH 7.4 over the time interval of more than their half‐life period (t_1/2). The amount of the drug loaded into the hydrogel also affected the dynamic release of the encapsulated drug. As expected, the gels showed a complete swelling‐dependent mechanism, which was further supported by the similar morphology of the swelling and release profiles of the drug‐loaded sample. The hydrophilic nature of the drug riboflavin does not contribute toward the zero‐order release dynamics of the hydrogel system. On the other hand, the swelling osmotic pressure developed between the gels and the external phase, due to loading of the drug by equilibration of the gels in the alkaline drug solution, plays an effective role in governing the swelling and release profiles. Finally, the minimum release of the drug in the swelling media of pH 2.0 and the maximum release with zero‐order kinetics in the medium of pH 7.4 suggest that the proposed drug‐delivery devices have a significant potential to be used as an oral drug‐delivery system for colon‐specific delivery along the gastrointestinal (GI) tract. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1133–1145, 2002; DOI 10.1002/app.10402     

Synthesis and characterization of novel pH‐responsive poly(2‐hydroxylethyl methacrylate‐co‐N‐allylsuccinamic acid) hydrogels for drug delivery

In this study, N‐allylsuccinamic acid (NASA) was synthesized in a single step with a yield of 85%. Carboxylic acid containing NASA was characterized through Fourier transform infrared (FTIR) radiation and ¹H‐NMR and ¹³C‐NMR analysis, and then it was used for synthesis of poly(2‐hydroxylethyl methacrylate‐co‐N‐allylsuccinamic acid) [p(HEMA‐co‐NASA)] hydrogels. The structure of the obtained pH‐responsive p(HEMA‐co‐NASA) hydrogels were characterized with FTIR spectroscopy and scanning electron microscopy analysis, and their swelling characterization was carried out under different drug‐release conditions. In the application step of the study, the hydrogels were used for the in vitro release of vitamin B12 and Rhodamine 6G, which were selected as model drugs. We determined that the hydrogels used as a drug‐delivery matrix could release the drug they had absorbed under different release conditions (phosphate‐buffered saline, 0.9% NaCl, and pH 1.2) at high rates for time periods of up to 24 h. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39660.     

Synthesis and swelling properties of 2‐hydroxyethyl methacrylate‐co‐1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine hydrogels

A series of 2‐hydroxyethyl methacrylate/1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine (HEMA/VSIB) copolymeric gels were prepared from various molar ratios of HEMA and the zwitterionic monomer VSIB. The influence of the amount of VSIB in copolymeric gels on their swelling behavior in water and various saline solutions at different temperatures and the drug‐release behavior, compression strength, and crosslinking density were investigated. Experimental results indicated that the PHEMA hydrogel and the lower VSIB content (3%) in the HEMA/VSIB gel exhibited an overshooting phenomenon in their dynamic swelling behavior, and the overshooting ratio decreased with increase of the temperature. In the equilibrium water content, the value increased with increase of the VSIB content in HEMA/VSIB hydrogels. In the saline solution, the water content for these gels was not affected by the ion concentration when the salt concentration was lower than the minimum salt concentration (MSC) of poly(VSIB). When the salt concentration was higher than the MSC of poly(VSIB), the deswelling behavior of the copolymeric gel was more effectively suppressed as more VSIB was added to the copolymeric gels. However, the swelling behavior of gels in KI, KBr, NaClO₄, and NaNO₃ solutions at a higher concentration would cause an antipolyelectrolyte phenomenon. Besides, the anion effects were larger than were the cation effects in the presence of a common anion (Cl^?) with different cations and a common cation (K⁺) with different anions for the hydrogel. In drug‐release behavior, the addition of VSIB increased the drug‐release ratio and the release rate. Finally, the addition of VSIB in the hydrogel improved the gel strength and crosslinking density of the gel. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2888–2900, 2001     

Water‐sorption and metal‐uptake behavior of pH‐responsive poly (N‐acryloyl‐N′‐methylpiperazine) gels

Hydrogels based on N‐acryloyl‐N′‐methylpiperazine (AcrNMP) swelled extensively in solutions of low pH due to the protonation of the tertiary amine. The water transport in the gels under an acidic condition was non‐Fickian and nearly Fickian in neutral pH with the collective diffusion coefficients determined as 2.08 × 10⁻⁷ and 5.00 × 10⁻⁷ cm⁻² s⁻¹, respectively. These gels demonstrated good metal‐uptake behavior with various divalent metal ions, in particular, copper and nickel, with the uptake capacity increased with increasing pH. The swelling ratio of the gel in the presence of metal ions decreased with increasing metal ion uptake. The results suggest that high metal ion uptake can lead to physical crosslinking arising from the interchain metal complex formation. The metal‐loaded gels could be stripped easily with 1M H₂SO₄ without any loss in their uptake capacity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 268–273, 2001     

Hydrogen Atom Attack on Fluorotoluenes: Rates of Fluorine Displacement

Rates of hydrogen atom attack on o-fluorotoluene (o-FTOL) and m-fluorotoluene (m-FTOL) at temperatures of 988–1144 K and pressures of 2–2.5 bar have been determined in a single-pulse shock tube study. Hydrogen atoms, generated from the decomposition of hexamethylethane, were allowed to react with the substrates and the characteristic products observed. Rate constants for two reaction channels, displacement of fluorine or methyl, were determined relative to displacement of methyl from 1, 3,5-trimethylbenzene (135TMB). Evidence is presented that abstraction of F is unimportant over the studied temperature range. With k(H + 135TMB → m-xylene + CH₃) = 6.7 × 10¹³ exp(–3255/T) cm³ mol⁻¹s⁻¹, the following rate expressions have been derived: k(H + o-FTOL → C₆H₅CH₃ + F) = 8.38 × 10¹³ exp(–6041/T) cm³ mol⁻¹s⁻¹; (1012–1142 K) k(H + o-FTOL → C₆H₅F + CH₃) = 2.37 × 10¹³ exp(–2938/T) cm³ mol⁻¹s⁻¹; (988–1142 K) k(H + m-FTOL → C₆H₅CH₃ + F) = 1.33 × 10¹⁴ exp(–6810/T) cm³ mol⁻¹s⁻¹; (1046–1144 K) k(H + m-FTOL → C₆H₅F + CH3) = 2.04 × 10¹³ exp(–3104/T) cm³ mol⁻¹s⁻¹; (1008–1144 K) Uncertainties in the relative rate constants are estimated to be factors of about 1.1, while the above absolute values have estimated expanded uncertainties of about a factor of 1.4 in rate, 10 kJ mol⁻¹ in the activation energy, and a factor of 3 in the A-factor. The present data are compared with relevant literature data. From our data and the thermochemistry, a model of the elementary steps comprising displacement of F is developed. On the basis of the model fit to our data, rate constants for the addition of atomic fluorine to toluene at 1100 K are derived. Rate expressions for fluorination reactions of toluene are also determined. The significance of the present results is discussed in the context of the formation of fluorinated byproducts in high-temperature systems.     

Kinetics of radiation‐induced grafting of 2‐hydroxyethyl methacrylate onto chloroprene rubber membrane and computer verification

Grafting of 2‐hydroxyethyl methacrylate(HEMA) onto chloroprene rubber(CR) membrane was carried out in ethanol by direct cobalt‐60 gamma ray irradiation. The kinetics of the grafting reaction was studied in respect of concentration of monomer, dose rate and temperature. The experimental results show that the functional relationship equation is dg₀/dt = k[M]^1.5 Ḋ. The apparent activation energy and collision frequency factor of the grafting polymerization are 46.2 kJ mol⁻¹ and 4.98 × 10⁷ mg cm⁻² kGy⁻¹ mol^−1.5 litre^1.5, respectively. The work established the relationship of the initial grafting rate (dg₀/dt) with various effect factors: ln (dg₀ dt) = 17.7 − 5560(1/T) + 1.5 ln [M] + ln Ḋ. This equation is also verified for the first time by a software named SMR, which function is using multiple linear regression to calculate the regression coefficient of a linear equation. © 1999 Society of Chemical Industry     

Drug diffusion in neutral and ionic hydrogels assembled from acetylated galactoglucomannan

In this study, hydrogels based on acetylated galactoglucomannan (AcGGM)—a hemicellulose present in softwood—were synthesized and examined for their properties in drug‐release systems using two model substances of different molecular weight, size, and polarity (caffeine and vitasyn blue). Neutral hydrogels were produced from functionalized AcGGM using hydroxyethyl methacrylate (HEMA) coupled via carbonyldiimidazole (CDI) and a co‐monomer in a radical‐initiated polymerization. Through a second modification reaction between the HEMA‐modified AcGGM (M‐AcGGM‐methacrylated AcGGM) and maleic anhydride, a “double‐modified” AcGGM (CM‐AcGGM‐carboxylated M‐AcGGM) was successfully formed that could be cross‐linked to form ionic hydrogels by the very same polymerization method. The neutral hydrogels showed drug release kinetics that could be easily regulated by changing the relative amount of the methacrylated AcGGM and its corresponding degree of methacrylation. The drug release rate and the Fickian swelling decreased with an increase in these two aforementioned parameters. The ionic hydrogels showed quicker release kinetics and higher swelling capabilities than the corresponding nonionic gels did, especially at neutral conditions. Under acidic conditions, the release speed was lowered as expected because of protonation of carboxylic functionalities. Based on the findings we conclude that these novel hemicellulose‐containing hydrogels have future prospects in drug release formulations, e.g., in a later stage of development for application in oral drug administration technology. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of drug loading on the properties of temperature‐responsive polyester–poly(ethylene glycol)–polyester hydrogels

Hydrogels that can undergo gelation upon injection in vivo are promising systems for the site‐specific delivery of drugs. In particular, some thermo‐responsive gels require no chemical additives but simply gel in response to a change from a lower temperature to physiological temperature (37 °C). The gelation mechanism does not involve covalent bonds, and it is possible that incorporation of drugs into the hydrogel could disrupt gelation. We investigated the incorporation of drugs into thermo‐responsive hydrogels based on poly(?‐caprolactone‐co‐lactide)‐block‐poly(ethylene glycol)‐block‐poly(?‐caprolactone‐co‐lactide) (PCLA–PEG–PCLA). Significant differences in properties and in the response to incorporation of the anti‐inflammatory drug celecoxib (CXB) were observed as the PEG block length was varied from 1500 to 3000 g mol^?1. Linear viscoelastic moduli of a PCLA–PEG–PCLA hydrogel containing a 2000 g mol^?1 PEG block were least affected by the incorporation of CXB and this gel also exhibited the slowest release of CXB, so the incorporation of phenylbutazone, methotrexate, ibuprofen, diclofenac and etodolac was also investigated for this hydrogel. Different drugs resulted in varying degrees of syneresis of the hydrogels, suggesting that they interact with the polymer networks in different ways. In addition, the drugs had varying effects on the viscoelastic and compressive moduli of the gels. The results showed that the effects of drug loading on the properties of thermo‐responsive hydrogels can be substantial and depend on the drug. For applications such as intra‐articular drug delivery, in which the mechanical properties of the hydrogel are important, these effects should thus be studied on a case‐by‐case basis. © 2019 Society of Chemical Industry     

Kinetic and thermodynamic studies on oxidative desulphurisation of organic sulphur from Indian coal at 50–150°C

This paper reports a relatively simple low-temperature non-isothermal oxidative desulphurisation of coal organic sulphur by weakening the CS bond using HgCl₂ solution to an inorganic sulphur-free high-sulphur Indian coal. When oxidised from 50°C to 150°C in air under normal atmospheric pressure, there is continuous decrease of organic sulphur content in the samples of the feed and Hg-treated coals. Desulphurisation is more in the Hg-treated coal (4.97–14.53 wt.%) than in the feed coal (3.72–10.93 wt.%). Kinetic study reveals that the oxidative desulphurisation process follows pseudo-first order kinetics and the rate constants have been found to be in the range (3.09–5.06)×10⁻⁵ s⁻¹ for feed coal and (4.19–6.80)×10⁻⁵ s⁻¹ for Hg-treated coal. The activation energies for the sulphur loss reaction in the oxidative desulphurisation process by using the pseudo-first order kinetic (feed coal: 2.21×10² J mol⁻¹; Hg-treated coal: 1.53×10² J mol⁻¹) have been found to be almost similar to those calculated by applying the Coats and Redfern's equation (feed coal: 2.19×10² J mol⁻¹; Hg-treated coal: 1.53×10² J mol⁻¹). However, the value is higher (feed coal: 3.50×10² J mol⁻¹; Hg-treated coal: 2.70×10² J mol⁻¹) when Horowitz and Metzger's equation is applied. The frequency factors computed by the pseudo-first order kinetics are very low and have been found to be 2.66×10⁻⁵ s⁻¹ for feed coal and 3.96×10⁻⁵ s⁻¹ for Hg-treated coal, suggesting very low rate of successful collisions for the formation of the activated complex. Evaluation of thermodynamic parameters viz., ΔH, ΔU, ΔS and ΔG, reveals that this oxidative desulphurisation process is non-spontaneous in nature and the degree of non-spontaneity of such a process in the feed coal is more relative to that of the Hg-treated coal.     

Thermooxidative degradation of poly(vinyl chloride)/acrylonitrile–butadiene–styrene blends

The thermal degradation process of poly(vinyl chloride)/acrylonitrile–butadiene–styrene (PVC/ABS) blends was investigated by dynamic thermogravimetric analysis in the temperature range 50–650°C in air. The thermooxidative degradation of PVC/ABS blends of different composition takes place in three steps. In this multistep process of degradation the first step, dehydrochlorination, is the most rapid. The maximal rate of dehydrochlorination for the PVC blends containing up to 20% ABS-modifier is achieved at average conversions of 23.5–20.0%, i.e., at 13.5% for the 50/50 blend. The apparent activation energies (E = 103–116 kJ mol⁻¹) and preexponential factors (Z = 2.11 × 10⁹−3.45 × 10¹⁰min⁻¹) for the first step of the degradation process were calculated after the Kissinger method. © 1996 John Wiley © Sons, Inc.     

The kinetics of isothermal nicotinamide release from poly(acrylic‐co‐methacrylic acid) loaded xerogel

The isothermal kinetics of in vitro nicotinamide release from poly(acrylic‐co‐methacrylic acid) loaded xerogel into water was evaluated. The isothermal kinetics curves of nicotinamide release from poly(acrylic‐co‐methacrylic acid) xerogel were measured at different temperatures ranging from 296 K to 315 K. It was proven that the kinetics of nicotinamide release from poly(acrylic‐co‐methacrylic acid) xerogel was a kinetically complex process which was neither controlled by the processes of drug diffusion nor with the relaxation of the xerogel. The kinetic of nicotinamide release from poly(acrylic‐co‐methacrylic acid) may be described by the kinetics model of reversible first order chemical reaction and the apparent activation energy have value of E_a,M = 14.1 kJ mol^?1 and preexponential factor ln(A_M min^?1) = 2.3. The rate constants of nicotinamide release ( ) and the rate constants of its reversible absorption reaction ( ) were calculated and found to fall within the range 0.019 min^?1?0.033 min^?1 for and 0.014 min^?1?0.016 min^?1 for . The value of activation energy for the nicotinamide releas, E_a.R =21.25 kJ mol^?1, is significantly higher than the value for the process of nicotinamide absorption (E_a,A = 2.6 kJ mol^?1). The rate of nicotinamide release was predetermined with the rate of nicotinamide molecules distribution between the hydrogel and surrounding solution. POLYM. ENG. SCI., 55:60–69, 2015. © 2014 Society of Plastics Engineers     

Kinetics of CO hydrogenation over coprecipitated cobalt–alumina

The kinetics of CO hydrogenation over coprecipitated 36 wt% Co/Al₂O₃ was studied in a fixed-bed microreactor at atmospheric pressure. Intrinsic kinetic data were obtained in the initial rate region using four different CO concentrations and two different H₂/CO ratios over the 473–523 K temperature range. The surface carbide mechanism with dissociative adsorption of hydrogen as the rate controlling step gives the most plausible kinetic model among the eight different models tested. C₁–C₄ production rates are found to be strongly influenced by temperature, and optimum C₁–C₄ hydrocarbon selectivity is obtained at 508 K. The activation energy for CO consumption and CH₄ formation are calculated as 74±2 kJ mol⁻¹ and 84±2 kJ mol⁻¹ respectively. ©1997 SCI     

Thermal degradation kinetics of thermotropic poly(p‐oxybenzoate‐co‐p,p′‐biphenylene terephthalate) fiber

An advanced heat‐resistant fiber (trade name Ekonol) spun from a nematic liquid crystalline melt of thermotropic wholly aromatic poly(p‐oxybenzoate‐p,p′‐biphenylene terephthalate) has been subjected to a dynamic thermogravimetry in nitrogen and air. The thermostability of the Ekonol fiber has been studied in detail. The thermal degradation kinetics have been analyzed using six calculating methods including five single heating rate methods and one multiple heating rate method. The multiple heating‐rate method gives activation energy (E), order (n), frequency factor (Z) for the thermal degradation of 314 kJ mol⁻¹, 4.1, 7.02 × 10²⁰ min⁻¹ in nitrogen, and 290 kJ mol⁻¹, 3.0, 1.29 × 10¹⁹ min⁻¹ in air, respectively. According to the five single heating rate methods, the average E, n, and Z values for the degradation were 178 kJ mol⁻¹, 2.1, and 1.25 × 10¹⁰ min⁻¹ in nitrogen and 138 kJ mol⁻¹, 1.0, and 6.04 × 10⁷ min⁻¹ in air, respectively. The three kinetic parameters are higher in nitrogen than in air from any of the calculating techniques used. The thermostability of the Ekonol fiber is substantially higher in nitrogen than in air, and the decomposition rate in air is higher because oxidation process is occurring and accelerates thermal degradation. The isothermal weight‐loss results predicted based on the nonisothermal kinetic data are in good agreement with those observed experimentally in the literature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1923–1931, 1999     

pH‐reversible hydrogels. IV. Swelling behavior of the 2‐hydroxyethyl methacrylate‐co‐acrylic acid‐co‐sodium acrylate copolymeric hydrogels

A series of 2‐hydroxyethyl methacrylate (HEMA) and sodium acrylate (SA50) copolymeric gels were prepared from HEMA and the anionic monomer SA50 with various molar ratios. The influence of SA50 on the copolymeric gels on their swelling behavior in deionized water at different temperatures and various pH buffer solutions was investigated. Results indicated that the poly(2‐hydroxyethyl methacrylate) (PHEMA) hydrogels exhibited an overshooting phenomenon in their dynamic swelling behavior. The maximum overshooting value decreased with increasing of the temperature. The same results were also found in the HEMA/SA50 copolymeric gels with a lower SA50 content. On the contrary, the overshooting phenomenon for HEMA/SA50 copolymeric gels with a higher content of SA50 was exhibited only under higher temperature (over 35°C). These copolymer gels were used to assess drug release and drug delivery in this article. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1360–1371, 2001     

Swelling behaviour of poly(α‐hydroxyacrylic acid) gel

Poly(α‐hydroxy acrylic acid) (PHA) and poly(acrylicacid) (PAA) gels were prepared by irradiating the respective 15 wt% aqueous solutions with γ‐rays. Swelling ratios for PHA gel were measured as a function of pH and divalent cation (Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺) concentration C₂ in the external solution to provide a comparison with the results for PAA gels. It was found that the swelling ratio of PHA gel steeply increases between pH 2 and 4, followed by a gradual swelling in the higher pH region. The corresponding steep swelling of PAA gel was observed at pH 3–6. Cation specificity in the equilibrium swelling ratio at a lower C₂ value (1.0 × 10⁻³ M) was approximately consistent with the binding selectivity in the solution system. Typically, the swelling ratio of PHA gel in the presence of Ca²⁺ was significantly lower than in the Mg²⁺ system, while the difference was slight for PAA gel. The response of the swelling ratio to changes in pH and C₂ was analysed as a first order relaxation to estimate the time constants. The (de)swelling kinetics measured by both the pH and C₂ jump were qualitatively interpreted in terms of main‐chain stiffness and intermolecular hydrogen bonding in the respective polymers. © 2000 Society of Chemical Industry