The effects of the pH value of the swelling medium on the kinetics of the swelling of a poly(acrylic acid) hydrogel

The isothermal kinetics curves of the swelling of a poly(acrylic acid) hydrogel in buffer solutions of different pH values (5, 7, and 9) at temperatures ranging from 30 to 40°C were determined. The possibilities of applying the Fick kinetics model and the Peppas equation were examined. It was found that the applicability of these models were limited. The kinetics model of a first‐order chemical reaction was found to describe the swelling kinetics of the PAA hydrogel in all the investigated buffer solution at all the investigated temperatures. Swelling kinetics is determined by the rate of expansion of the network. The kinetic parameters (E_a, ln A) of the swelling of the PAA hydrogel in buffer solutions of different pH values were determined. The activation energy and the pre‐exponential factor of the swelling of the PAA hydrogel in buffer medium decreased with increasing pH value of the swelling medium. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The effect of primary structural parameters of poly(methacrylic acid) xerogels on the kinetics of swelling

Xerogels of poly(methacrylic acid) (MAXG) with different primary structural parameters (PSP) [number average molar mass between the network crosslinks (M_c), the crosslink degree (ρ_c), and the distance between the macromolecular chains (d)] are successfully synthesized by crosslinking free‐radical polymerization. The isothermal swelling curves of synthesized MAXG are measured in distilled water in the temperature range of 25–40°C. The swelling conversion curves of all the MAXG may be described with kinetics model of phase boundary controlled reaction, i.e., contracting area (R2). The values of swelling kinetics parameters (E_a and lnA) linearly increase with the increase in M_c. This work presented a novel and quantum model of the mechanism of xerogel's swelling activation process based on resonant coupling of vibration oscillation of water molecules and vibration modes of xerogel. A quantum nature of E_a of swelling process is proved and explained the effects of PSP on the values of swelling kinetics parameters. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Genipin‐cross‐linked chitosan‐based hydrogels: Reaction kinetics and structure‐related characteristics

The main aim of this work is the synthesis and characterization of cross‐linked chitosan systems. Chitosan hydrogels can be prepared by physical or chemical cross‐linking of polymer chains. Chemical cross‐linking, leading to the creation of hydrogel networks possessing improved mechanical properties and chemical stability, can be achieved using either synthetic agents or natural‐based agents. In this work, the cross‐linker Genipin, a naturally derived compound, was selected because of the lower acute toxicity compared to many other commonly used synthetic cross‐linking reagents. In particular, the chemical stabilization of chitosan through genipin cross‐linking molecules was performed and characterized by calorimetric analyses (differential scanning calorimetry), swelling measurements in different pHs, and ionic strength. The reaction kinetics was carried out by means of rheological measurements, and both the activation energy (E_a) and the reaction order (m) were calculated. The hydrogel analyses were carried out at different concentrations of genipin (GN1 and GN2). The results were used to evaluate the possibility to use the chemical cross‐linked chitosan–genipin hydrogel for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42256.     

Influence of microwave heating on the kinetic of acrylic acid polymerization and crosslinking

Kinetics of isothermal formation of poly (acrylic acid) (PAA) hydrogels through polymerization of acrylic acid and crosslinking of the PAA formed in a conventionally heated reaction system and in a microwave heated reaction system were investigated. It was found that in the microwave heated system the reaction rate constant of PAA hydrogel formation significantly increased (from 32 to 43 times) when compared with the conventionally heated system. The isothermal kinetics of the PAA hydrogel formation during the microwave process could be described by the so‐called first‐order chemical reaction kinetics model. In contrast, the so‐called second‐order chemical reaction rate model could best describe the isothermal kinetics of the PAA hydrogel formation during the conventionally heated process. Also, in the microwave heated system, the reaction kinetics of the PAA hydrogel formation and its kinetic parameters changed, that is, the activation energy (E_a) decreased by about 19% and the pre‐exponential factor (lnA) decreased by 2.2 times. The decrease in activation energy, change in entropy of activation energy, and decrease in the pre‐exponential value of PAA hydrogel formation under microwave heating are caused with increased energy of the reactive species when compared with their energy in thermal activation. Increased energy of the reactive species is a consequence of rapid transfer and absorption of the energy of microwave field to the existing reactive species. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Kinetics of Isothermal Ethanol Adsorption onto a Carbon Molecular Sieve under Conventional and Microwave Heating

The isothermal kinetics of ethanol adsorption from aqueous solution onto a zeolite type carbon molecular sieve (CMS‐3A) under conventional heating (CH) and microwave heating (MWH) was investigated. The adsorption kinetics is described by the model of a phase‐boundary controlled reaction for both heating modes. The activation energy (E_a) for the adsorption process under MWH is lower than under CH while the preexponential factor (lnA) is higher. Ethanol adsorption is a kinetically complex process whose complexity changes with the mode of heating. The established decrease in E_a and increase in lnA under MWH compared to CH is explained with the increase in the ground vibrational level of the – OH twisting vibrations in the ethanol molecule and with the decrease in its anharmonicity factor which is caused by the selective resonant transfer of energy from CMS‐3A to the OH oscillators.     

The effects of microwave heating on the kinetics of isothermal dehydration of equilibrium swollen poly(acrylic‐co‐methacrylic acid) hydrogel

The isothermal dehydration of poly(acrylic‐co‐methacrylic acid) (PAM) hydrogel under microwave heating (MWH) was investigated. The isothermal kinetics curves of the PAM hydrogel dehydration at temperature range from 293 K to 333 K were recorded. Based on the differential isoconversion method it was concluded that the microwave dehydration of poly(acrylic‐co‐methacrylic acid) hydrogel is an elementary kinetics process. Applying the model‐fitting method it was established that the kinetics of microwave isothermal hydrogel dehydration can be described by the kinetics model of the phase‐boundary controlled process (contracting area). The values of the kinetics parameters (activation energy (E_a) and preexponential factor (lnA)) of the dehydration process under microwave heating are lower than the values for conventional heating (CH). The established influence of MWH on the kinetics of hydrogel dehydration is explained with a specific activation mechanism of water molecules for dehydration and with the increase in the value of the energy of the ground level of the resonant oscillator of water molecule (v = 837 cm^?1) due to the absorption of microwave energy. POLYM. ENG. SCI., 56:87–96, 2016. © 2015 Society of Plastics Engineers     

Analysis of the swelling dynamics of crosslinked P(N‐iPAAm‐co‐MAA) copolymers,the corresponding homopolymers and their interpenetrating networks. Kinetics of water penetration into the gel above the pKaof MAA comonomeric units

The effect of composition on the swelling kinetics of a series of crosslinked poly(N‐isopropylacrylamide)s [P(N‐iPAAm)] and poly(methacrylic acid)s [P(MAA)], their statistical copolymers P(N‐iPAAm‐co‐MAA), and some sequential interpenetrating networks (IPNs) has been studied at pHs above the pK_a of MAA comonomeric units. The swelling process of the hydrogels upon immersion in buffer solutions was monitored by the weight change as a function of time. First‐order kinetics apply better than second‐order kinetics which fail, especially for predicting swelling equilibrium values. However, hydrogels presenting hydrogen bonding between MAA and N‐iPAAm units do not obey either first‐order or second‐order kinetics. The high n values found indicate that the swelling process is mostly controlled by polymer relaxation. Copyright © 2003 Society of Chemical Industry     

Preparation and swelling characterization of poly (n‐isopropylacrylamide)‐based porous hydrogels

Nine different poly(n‐isopropylacrylamide)‐based hydrogels, including nonionic, cationic, and anionic hydrogels, were synthesized in with and without the addition of pore‐forming agents. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observations, and the determination of the swelling ratio swelling kinetics. All the results showed that the cationic hydrogels had faster swelling kinetics than the anionic and nonionic hydrogels. The addition of pore‐forming agents (NaHCO₃ and carboxymethylcellulose) during the synthesis process led to porous hydrogels with lower dry densities, swelling ratios, and swelling kinetic parameter values. An empirical equation was developed to successfully correlate the swelling kinetic parameter with the hydrogel swelling ratio. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3651–3658, 2004     

Kinetics study of isothermal nicotine release from poly(acrylic acid) hydrogel

The isothermal kinetic of the release of nicotine from a poly(acrylic acid) (PAA) hydrogel was investigated at temperature range from 26°C to 45°C. Specific shape parameters of the kinetic curves, the period of linearity and saturation time were determined. The change in the specific shape parameters of the kinetic curves with temperature and the kinetic parameters of release of nicotine E_a and ln A were determined. By applying the “model fitting” method it was established that the kinetic model of release of nicotine from the PAA hydrogel was [1 − (1 − α)^1/3] = k_Mt. The limiting stage of the kinetics release of nicotine was found to be the contracting volume of the interaction interface. The distribution function of the activation energy was determined and the most probable values of activation energies of 25.5 kJ mol⁻¹ and 35 kJ mol⁻¹ were obtained. Energetically heterogeneity of the interaction interface was explained by the existence of the two different modes of bonding the nicotine molecules onto the hydrogel network by hydrogen bond and electrostatic forces. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Moisture curing kinetics of isocyanate ended urethane quasi‐prepolymers monitored by IR spectroscopy and DSC

The study of the kinetics of the curing of isocyanate quasi‐prepolymers with water was performed by infrared spectroscopy and differential scanning calorimetry. The influence of the free isocyanate content, polyol functionality, and of the addition of an amine catalyst (2,2′‐dimorpholinediethylether) in the reaction kinetics and morphology of the final poly(urethane urea) was analyzed. A second‐order autocatalyzed model was successfully applied to reproduce the curing process under isothermal curing conditions, until gelation occurred. A kinetic model‐free approach was used to find the dependence of the effective activation energy (E_a) with the extent of cure, when the reaction was performed under nonisothermal conditions. The dependence of E_a with the reaction progress was different depending on the initial composition of the quasi‐prepolymer, which reveals the complexity of the curing process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Chemically clean synthesis and characterization of graphene oxide‐poly(acrylic acid–sodium styrene sulfonate) composite thermostable elastic gel encapsulating copper nanoparticles for efficient catalytic reduction of 4‐nitrophenol

The thermostable chemically blended elastic poly‐(acrylic acid–sodium‐styrene‐sulfonate–graphene oxide) super‐absorbent hydrogel was synthesized by additive‐free gamma‐radiation induced polymerization followed by crosslinking method. It showed the best swelling ratio in water due to its porous nature. The composite material adsorbed 98 mg/g Cu(II) at room temperature from the aqueous solution of Cu(II) at pH 5 by the chemi‐adsorption of Cu(II) ions at several energetically heterogeneous functional groups. The copper nanoparticles (CuNPs) of size 12 ± 8 nm had been synthesized in situ by chemical reduction of the pre‐adsorbed Cu(II) ions. The functional groups of composite hydrogel served as complexing agent and nano‐reaction sites. Avoiding any pre‐reduction induction time, the inexpensive CuNPs catalytically completely decolorized the aqueous solution of 4‐nitrophenol (4‐NP) within 60 s in the presence of NaBH₄ at a promising calculated rate constant (9.0 × 10^?2/s) ever reported in the literatures. It is in contrast to the commonly noticeable phenomenon for other CuNPs‐based catalysis of 4‐NP. The composite hydrogel matrix helped to retain the catalytic activity of CuNPs and simultaneously it helped in the osmotic inclusion of 4‐NP into the reaction cites. This composite hydrogel synthesized through a chemically clean method could be utilized for efficient conversion of hazardous chemical 4‐NP to industrially important chemical 4‐aminophenol. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46200.     

Synthesis,characterization, and swelling behavior of superabsorbent hydrogel from sodium salt of partially carboxymethylated tamarind kernel powder‐g‐PAN

Polyacrylonitrile (PAN)‐grafted sodium salt of partially carboxymethylated tamarind kernel powder (Na‐PCMTKP‐g‐PAN, %G = 413.76 and %GE = 96.48) was prepared using the established optimal reaction conditions for ceric‐initiated graft copolymerization of acrylonitrile onto Na‐PCMTKP (DS = 0.15) in a homogeneous medium. The graft copolymer was hydrolyzed by 0.7N KOH solution at 90–95°C to yield the superabsorbent hydrogel H‐Na‐PCMTKP‐g‐PAN. The nitrile groups of Na‐PCMTKP‐g‐PAN were completely converted into a mixture of hydrophilic carboxamide and carboxylate groups during alkaline hydrolysis, followed by in situ crosslinking of the grafted PAN chains. The products were characterized spectroscopically and morphologically. The swelling behavior of the unreported superabsorbent hydrogel, H‐Na‐PCMTKP‐g‐PAN, was studied by carrying out its absorbency measurements in low‐conductivity water, 0.15M salt (NaCl, CaCl₂, and AlCl₃) solutions, and simulated urine (SU) at different timings. The swelling behavior of the hydrogel in different swelling media followed the second‐order kinetics. The values of the various swelling characteristics were reported. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Swelling mechanism of porous P(VP‐co‐MAA)/PNIPAM semi‐IPN hydrogels with various pore sizes prepared by a freeze treatment

BACKGROUND: The objective of the work reported was to investigate the effect of gel microstructure on the swelling mechanism. A series of porous gels with various pore sizes were prepared by freeze‐treating a conventional hydrogel that contained various amounts of water at ? 20 °C. Scanning electron microscopy and differential scanning calorimetry were used to characterize the microstructure of the porous gels. RESULTS: The experimental results showed that the water content during freezing was the key factor controlling the microstructure. Measurement of swelling kinetics showed that a greater amount of water during the freezing process would lead to a rapid swelling rate. The apparent diffusion coefficients (D_p) at all times during the swelling process were obtained by fitting the experimental data to the diffusion equation. The values of D_p suggested that the swelling mechanism of the gels depends on the pore size. The diffusion exponent (n) obtained by fitting the fractional mass change (M_t/M_∞) to equation of Fick's law further confirmed that the swelling mechanism of the gels is determined by the pore size. CONCLUSION: The swelling mechanism of the gels is determined by the microstructure related to the pore size and the thickness of struts. The microstructure can be controlled by adjusting the water content of the hydrogels by changing the pH of the swelling medium prior to freezing. Copyright © 2008 Society of Chemical Industry     

Self assembled hydrophobic nanoclusters of poly(methyl methacrylate) embedded into polyvinyl alcohol based hydrophilic matrix: Preparation and water sorption study

Hydrophilic matrices containing nanosized clusters of hydrophilic moieties have demonstrated potential applications in biomedical field. A novel hydrogel containing nanosized domains (20–35 nm) of hydrophobic moieties of poly(methyl methacrylate) (PMMA) was prepared by grafting crosslinked poly(acrylic acid‐co‐methyl methacrylate) chains onto polyvinyl alcohol (PVA) backbone using an efficient redox system. The graft copolymerization process was investigated to observe the influence of gel components on the kinetic parameters of grafting such as rate of grafting (R_g), grafting yield (G_y) and grafting efficiency (G_e). The prepared graft nanohydrogel was evaluated for its water sorption potential under varying chemical composition of the gel and changing pH, temperature, and ionic strength of the swelling bath. The swelling process was also examined mechanistically and diffusion constants (D) of water molecules through the swellable nanohydrogel were also evaluated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Grafted CMC/silica gel superabsorbent composite: Synthesis and investigation of swelling behavior in various media

In the present study, we attempt to synthesize and characterize novel CMC-g-poly (acrylic acid-co-2-acrylamido-2-methylpropanesulfonic acid)/silica gel composite. Infrared spectroscopy and TGA thermal analysis were carried out to confirm the chemical structure of the hydrogel. Moreover, morphology of the samples was examined by scanning electron microscopy. The effect of reaction variables affecting on water absorbency of the composite and swelling behavior in various solvents, salt, and pH solutions was investigated. Maximum water absorbency of the optimized final product was found to be 4000 g/g in distilled water. The absorbency under load (AUL) of the hydrogel was also determined by using an AUL tester at various applied pressures. Finally, dynamic swelling kinetics of the hydrogel was studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of poly(acrylic acid) xerogel structure on swelling kinetics in distilled water

Summary The basic structural properties of xerogels of crosslinked poly(acrylic acid) were defined and determined: xerogel density (ρ_xg), xerogel volume fraction in the equilibrium-swollen state (v₂), the number average molar mass between network crosslinks , the crosslink density (ρ_c) and the distance between macromolecular chains (d). A crosslinking ratio (X) increase leads to a linear increase in the values for ρ_xg and ρ_c, while the values and d decrease. The isothermal swelling kinetic curves of four samples of structurally different poly(acrylic acid) xerogels in bidistilled water at different temperatures ranging from 25 to 45 °C were determined. It is shown that isothermal kinetic swelling curves could not be described with the model of first-order reaction kinetics in entire. It was found that these curves could be described by the Johanson-Mampel-Avrami (JMA) equation. For all of the investigated xerogel samples, the initial swelling rate (v_in), effective reaction rate constant (k) and equilibrium swelling degree increased with swelling temperature increase. Based on the determined values of the v_in and k, the activation energy (E_a) and pre-exponential factor (lnA) were determined. It was concluded that the activation energy linearly increased with increasing distance between macromolecular chains (d) and molar mass between the network crosslinks . The relationship between the activation energy changes with pre-exponential factor (compensation effect) caused by xerogel structural properties was established. Isothermal swelling kinetics could be completely described by the kinetics of phase transition of the xerogel transformation from glassy to rubbery state, i.e. with the JMA kinetic equation.     

Preparation and application in drug controlled delivery of pH‐sensitive P(CE‐co‐DMAEMA‐co‐MEG) hydrogel

A pH‐sensitive hydrogel [P(CE‐co‐DMAEMA‐co‐MEG)] was synthesized by the free‐radical crosslinking polymerization of N,N‐dimethylaminoethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate(MPEG‐Mac) and methoxyl poly(ethylene glycol)‐poly(caprolactone)‐methacryloyl methchloride (PCE‐Mac). The effects of pH and monomer content on swelling property, swelling and deswelling kinetics of the hydrogels were examined and hydrogel microstructures were investigated by SEM. Sodium salicylate was chosen as a model drug and the controlled‐release properties of hydrogels were pilot studied. The results indicated that the swelling ratios of the gels in stimulated gastric fluids (SGF, pH = 1.4) were higher than those in stimulated intestinal fluids (SIF, pH = 7.4), and followed a non‐Fickian and a Fickian diffusion mechanism, respectively. In vitro release studies showed that its release rate depends on different swelling of the network as a function of the environmental pH and DMAEMA content. SEM micrographs showed homogenous pore structure of the hydrogel with open pores at pH 1.4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40737.     

Adsorption of methylene blue on hemicellulose‐based stimuli‐responsive porous hydrogel

A stimuli‐responsive porous hydrogel was synthesized from wheat straw hemicellulose using CaCO₃ as the porogen, and its application for the removal of methylene blue was studied. The porous structure of the prepared hydrogel was confirmed by SEM analysis. The effects of pH and polyelectrolyte on the swelling of the hydrogels were discussed, and the porous hydrogels showed excellent sensitivity to pH and salt. The deswelling kinetic study indicated that the hydrogels exhibited rapid shrinking in NaCl aqueous solutions. The methylene blue adsorption on the hydrogels was investigated, and the obtained adsorption data was fitted to the pseudo‐first‐order, pseudo‐second‐order and intra‐particle diffusion kinetics models, and the pseudo‐first‐order kinetic model could describe the adsorption process, and the adsorption process of methylene blue on the hydrogels was controlled by external film diffusion. This study reported that the hemicellulose‐based porous hydrogel is promising for water treatment. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41606.     

Study of the ammonia decomposition over iron catalysts

The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k₀ exp (Ea/RT)pNH₃. The activation energy of the ammonia decomposition process has been found for samples with potassium as E _a= 96 kJ/mol, for samples without potassium as E _a= 87 kJ/mol. This revised version was published online in July 2006 with corrections to the Cover Date.     

Modified carrageenan. 4. Synthesis and swelling behavior of crosslinked κC‐g‐AMPS superabsorbent hydrogel with antisalt and pH‐responsiveness properties

To synthesize a novel biopolymer‐based superabsorbent hydrogel, 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) was grafted onto kappa‐carrageenan (κC) backbones. The graft copolymerization reaction was carried out in a homogeneous medium and in the presence of ammonium persulfate (APS) as an initiator, N,N,N′,N′‐tetramethyl ethylenediamine (TMEDA) as an accelerator, and N,N′‐methylene bisacrylamide (MBA) as a crosslinker. A proposed mechanism for κC‐g‐AMPS formation was suggested and the hydrogel structure was confirmed using FTIR spectroscopy. The affecting variables on swelling capacity, i.e., the initiator, the crosslinker, and the monomer concentration, as well as reaction temperature, were systematically optimized. The swelling measurements of the hydrogels were conducted in aqueous solutions of LiCl, NaCl, KCl, MgCl₂, CaCl₂, SrCl₂, BaCl₂, and AlCl₃. Due to the high swelling capacity in salt solutions, the hydrogels may be referred to as antisalt superabsorbents. The swelling of superabsorbing hydrogels was measured in solutions with pH ranging 1 to 13. The κC‐g‐AMPS hydrogel exhibited a pH‐responsiveness character so that a swelling–deswelling pulsatile behavior was recorded at pH 2 and 8. The overall activation energy for the graft copolymerization reaction was found to be 14.6 kJ/mol. The swelling kinetics of the hydrogels was preliminarily investigated as well. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 255–263, 2005