Study on the swelling kinetics of superabsorbent using open circuit potential measurement

Open circuit potential measurement was used to trace the swelling kinetics of superabsorbent. The calibration curve and its fitting result showed the validity of the method in determining the concentration of chloride ion in aqueous solution. According to the regression analysis and theoretical derivation, the relationship between the open circuit potential change and the swelling ratio was obtained. Comparing with tea bag method, it was verified that open circuit potential measurement could be employed to trace the swelling kinetics of superabsorbent. The hysteresis effect of solute entering into superabsorbent and the overflow of soluble parts of hydrogel were also observed. Besides, we found that the entrance of solute and water were almost synchronal, and the concentration of solution absorbed by superabsorbent was lower than that of swelling medium. Moreover, the swelling model of superabsorbent in salting liquid was slightly modified.     

Gel strength and swelling of acrylamide‐protic acid superabsorbent copolymers

The viscoelastic and swelling properties of polyacrylamide‐based superabsorbent copolymers were investigated as a function of the ionic comonomer structure. Superabsorbent copolymers were synthesized by free‐radical crosslinking copolymerization of acrylamide and one of the monoprotic acids (acrylic acid and crotonic acid) or the diprotic acids (maleic acid and itaconic acid) as the investigated ionic comonomer. The reaction composition of all components, i.e. monomer, comonomer, initiator, co‐initiator, and crosslinker, was fixed to be the same for the synthesis of all four superabsorbent copolymer systems. Viscoelastic measurements were performed in all systems where the particles were closely packed. The network structures of all systems were evaluated via viscoelastic and swelling measurements. The results indicated that superabsorbent polymers (SAPs) with high water absorbency were accompanied by low gel strength and the calculated high value of molecular weight between crosslinks ($\bar {M}{}_c$ ) and low value of effective crosslinking density (ν_e). Diprotic acid‐containing SAPs showed higher water absorbency over monoprotic acid‐containing and non‐ionic ones. The differences in $\bar {M}{}_c$ and ν_e values of each system were explained with respect to the differences in the monomer reactivity ratio and hydrophilicity of the comonomers. Copyright © 2010 John Wiley & Sons, Ltd.     

Needleless electrospinning of poly(acrylic acid) superabsorbent: Fabrication,characterization and swelling behavior

In this work, nanofibrous hydrogel has been fabricated from needleless electrospinning of Poly(acrylic acid) (PAA) in an aqueous solution with different concentrations. First, all solution samples were characterized for pH, surface tension, conductivity and viscosity. Next, electrospinnability of the PAA-water dope solution was investigated using the needleless electrospinning technique under constant conditions. Results indicated that the PAA-water solution was not electrospinnable. Therefore, the neutralization of carboxylic groups in the PAA chemical structure using the NaOH solution was investigated to enhance the PAA electrospinnability. Morphology observation revealed that the fiber diameters ranged from 40 to 250 nm and increased with increasing the solution concentrations. Increasing the neutralization degree (10%, 15% and 20% with 50 wt% NaOH solution) led to increase the dope viscosity and conductivity. The resultant nanofibers could be rendered water-insoluble by incorporating 1,4-butanediol diglycidyl-ether in the PAA-water dope solution, then heat-induced crosslinking was performed using a microwave at different curing times (1–5 min) and temperatures (45–105 °C). The nanofibrous hydrogel mat was then characterized by FTIR. The resulting nanofibrous hydrogel showed remarkable water absorption capacity up to 17,000% and 51,000% (within 15 min) in the standard saline solution and distilled water, respectively.     

Relationship between swelling and mechanical properties of cross-linked polymers mixed with sand

Cross-linked polymers consisting of acrylamide, sodium acrylate, starch fragments and a cross-linker were synthesized with the same content of carboxyl groups and three degrees of cross-linking Q of 0.04, 0.2 and 1 wt%. An increase in Q gradually reduces the swelling of polymer gels in water; when distributed in sand, polymer gels exhibit maximum swelling at Q = 0.2 wt%. It is shown that the behavior of polymer gels in sand is determined by the balance between the elasticity of swollen polymer gels and the resistance of sand particles     

Understanding of nanogels swelling behavior through a deep insight into their morphology

A thorough understanding of the morphology of the environmental sensitive nanogels was indispensable to obtain a deeper insight on their stimuli‐responsive behavior. Therefore, in this work the colloidal characterization and the study of the inner morphology were related by using light scattering technique and ¹H‐nuclear magnetic resonance transverse relaxation measurements combined with the Flory–Rehner theory. Different biocompatible and dual‐stimuli‐sensitive nanogel particles based on poly(2‐diethylaminoethyl) methacrylate were synthesized using three different crosslinkers: two bifunctional and one multifunctional. All the nanogels obtained had a core–shell type heterogeneous morphology, but they presented completely different swelling behaviors due to their different crosslinking points’ distribution and polymeric chains’ microstructure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2017–2025     

Dynamic and equilibrium swelling of a sulfonic acid superabsorbent copolymer in salt solutions

Superabsorbent copolymers were synthesized by free radical reverse emulsion from the monomers acrylamide and 2‐acrylamido‐2‐methyl‐propanosulfonic acid with a divinyl crosslinker (methylene‐bisacrylamide). The copolymer synthesized was then identified by Fourier transform infrared spectroscopy, its porosity was examined by electronic microscopy, and its specific gravity was determined by the conventional procedure. The dynamic and equilibrium swelling behavior of the copolymer was studied, in water and in salt solutions, at 25 °C (chlorides and sulfates of sodium and magnesium). As to the equilibrium swelling, the influence of the pH as well as of the salt type and its concentration was observed. As to the dynamic swelling, it was interpreted in terms of both a simple power of time equation, and a more detailed model based on a coupled diffusion‐relaxation mechanism. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 505–514, 2004     

Synthesis and characterization of biodegradable network hydrogels having both hydrophobic and hydrophilic components with controlled swelling behavior

A new class of biodegradable hydrogels, consisting of hydrophobic poly(D ,L )lactic acid (PDLLA) and hydrophilic dextran segments with a polymer network structure, was synthesized with UV photopolymerization. Unsaturated vinyl groups first were introduced onto the PDLLA and dextran polymer backbones, then followed by a crosslinking reaction of diacrylate-terminated PDLLA and dextran acrylate. The chemical crosslinking forced the hydrophobic PDLLA and hydrophilic dextran segments to mix with each other in the network hydrogels. The new polymers were characterized by standard polymer characterization methods such as NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. The effects of reaction time, temperature, and molar ratio of the reactants on the incorporation of acrylate onto the polymer backbone were examined. A series of hydrogels with different dextran/PDLLA composition ratios was prepared, and their swelling behaviors were studied. These new bicomponent network hydrogels had a wide range of hydrophilicity to hydrophobicity that was difficult to achieve in totally hydrophilic hydrogels. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4554–4569, 1999     

Complex pH- and temperature-sensitive swelling behavior of mixed polymer brushes

The ability of a mixed polymer brush consisting of poly(N-isopropyl acrylamide) (PNIPAAM) and poly(acrylic acid) (PAA) to modify physicochemical interfacial properties is presented. The answer of the binary brush toward changes of environmental conditions like temperature, salt concentration, and pH value was investigated by in situ spectroscopic VIS-ellipsometry as well as AFM and contact angle mesurements in the dry state and compared with the behavior of the corresponding homopolymer brushes. A coupled swelling of PNIPAAm and PAA could be found, leading to a complex pH-, salt-, and temperature-sensitive swelling behavior of these mixed brushes, also depending on the composition of the brush. The complex interaction of the two polymers resulted in new properties of the mixed system. Although the temperature sensitivity of the mixed system was decreased compared with that of the corresponding PNIPAAM brushes, the sensitivity toward pH and salt concentration was amplified compared with that of pure PAA brushes. Additionally it is shown that in spite of the decreased temperature sensitivity of the mixed brush, a temperature-dependent adsorption of human serum albumin was observed whereas an increased adsorption affinity was found that is not predictable from the adsorption affinity of the corresponding homopolymer brushes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1606–1615, 2010     

Synthesis and characterization of biodegradable hydrophobic–hydrophilic hydrogel networks with a controlled swelling property

A biodegradable polymer network hydrogel system with both hydrophilic and hydrophobic components was synthesized and characterized. The hydrophilic and hydrophobic components were dextran and poly(D,L )lactic acid (PDLLA), respectively. These two polymers were chemically modified for incorporating unsaturated groups for subsequent UV crosslinking to generate a hydrogel with a three‐dimensional network structure. The effects of the reaction conditions on the synthesis of a dextran derivative of allyl isocyanate (dex‐AI) were studied. All newly synthesized materials were characterized by Fourier transform infrared and NMR. The swelling property of the hydrogels was studied in buffer solutions of different pHs. The results of this study showed that a wide‐range swelling property was obtained by changes in the dex‐AI/PDLLA composition ratio, the type and degree of unsaturated groups incorporated into dextran, and the UV photocrosslinking time. The solvent extraction effect on the swelling property of the hydrogels was also studied. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2392–2404, 2000     

Modeling on swelling behavior of a confined polymer network

Polymeric membranes suffer from plasticization in gas separation, extensive swollen in pervaporation, nanofiltration, and fuel cells by losing performance. Growing research has experimentally realized that the membrane performance could be stabilized by blending with inert second polymer or imbedding in a porous inert confinement. In this article, we introduce a generic model based on Flory–Rehner's swelling theory to describe various membrane processes using a measurable parameter. We assume the membrane polymer to be a network and the constraint as an expandable structure with an energy density equal to its E‐Modulus. The model reveals that the isotropic constraint is far more efficient in swelling control. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1589–1593, 2008     

Use of a superabsorbent polymer for the preconcentration of volatile components from complex matrices

A polymeric material commonly used as a superabsorbent in the sanitary industry is proposed for the first time for analytical purposes. Specifically, we have evaluated in this work the possibility of using this material in a programmed-temperature vaporizer (PTV) injector for the introduction of large volume samples. To that end, the viability of this superabsorbent polymer as a retaining material was first studied by testing the stability of its absorption capacity in the presence of various solvents and at various temperatures. Subsequently, its effectiveness in the isolation of menthol and its isomers from Mentha piperita essential oil as well as gamma-lactones from peach essential oil was assessed. For that purpose, optimization of different variables, namely PTV temperatures during sampling, purge times, and desorption temperatures, involved in the solvent elimination was performed. Additionally, the information obtained was compared with that acquired for the adsorbent material Tenax TA. The results shown in this work proved not only the viability of using this superabsorbent polymer in analytical procedures but also demonstrated its advantages over the adsorbent Tenax TA in attaining internal GC concentration of a sample by introducing large volumes via PTV.     

Simultaneous in situ measurement of sorption and swelling of polymers in gases and supercritical fluids

In this work, a novel method to simultaneously measure in situ swelling and sorption of gases and supercritical fluids in polymers in a commercially available apparatus is proposed. A gravimetric approach reported recently is applied to measure sorption whereas swelling is determined in situ by direct visualization. The proposed method has been used to study the sorption and swelling of carbon dioxide in poly (methyl methacrylate) and the obtained results are compared to previously published literature data. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

A novel method for the synthesis of the PEG-crosslinked chitosan with a pH-independent swelling behavior

In this study, a simple method was developed to crosslink chitosan using poly(ethylene glycol) (PEG) with different molecular weights. Crosslinking of chitosan was confirmed by various spectral analyses. The differential scanning calorimetric (DSC) study indicated that the rigid crystalline structure of chitosan was decreased after crosslinking with PEG. The PEG-crosslinked chitosan (PEG-Ch) showed a pH-independent swelling behavior: swelled in both the simulated stomach (pH 1.1) and intestinal (pH 7.4) solutions. The swelling ratio of PEG-Ch increased significantly with a higher molecular weight of PEG used. In contrast, chitosan dissolved completely in a simulated stomach solution and showed a comparatively less swelling in a simulated intestinal solution. Thus, the prepared PEG-Ch could be a better biomaterial than chitosan in the development of orally sustained drug-delivery devices.     

Synthesis and electrochromic properties of a new family of methacrylate polymers containing pendant oligothiophenes

A new family of methacrylate polymers containing pendant terthiophene, quaterthiophene, quinquethiophene, and sexithiophene was synthesized by the radical polymerization of the corresponding methacrylate monomers, and the electrochemical and electrochromic properties were investigated. The anodic oxidation of these polymers in the presence of tetra‐n‐butylammonium perchlorate as a supporting electrolyte produced radical‐cation salts of pendant oligothiophenes with ClO as a dopant. The electrochemically oxidized polymers had partially crosslinked structures resulting from the coupling reaction of pendant oligothiophene radical cations, the extent of crosslinking significantly decreasing with the increasing conjugation length of the pendant oligothiophenes. Comparative spectroelectrochemical studies of the monomers in solution and the polymers as solid films showed that π‐dimer formation of oligothiophene radical cations took place more readily for the polymer films than for the monomers in solution. This new family of methacrylate polymers containing pendant oligothiophenes constitutes a new class of potential electrochromic materials, undergoing reversible, clear color changes on electrochemical oxidation and reduction. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2471–2484, 2003     

Synthesis and thermal and spectroscopic properties of macrocyclic vinyl aromatic polymers

Well‐defined and narrow molecular weight distribution macrocyclic poly(2‐vinylnaphthalene) (P2VN) and poly(2‐vinyl‐9,9‐dimethylfluorene) (PDMVF) containing a single 1,4‐benzylidene or 9,10‐anthracenylidene unit have been synthesized via the potassium naphthalide initiated polymerization of the monomers followed by the end‐to‐end coupling of the resulting P2VN dianions under high‐dilution conditions with 1,4‐bis(bromomethyl)benzene or 9,10‐bis(chloromethyl)anthracene. Molecular characterization has been carried out by size exclusion chromatography, nuclear magnetic resonance, differential scanning calorimetry, ultraviolet–visible spectroscopy, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The thermal properties show distinct differences between the cyclic and matching linear polymers, with the macrocycles showing much higher glass‐transition and decomposition temperatures. The absorption bands are both hyperchromic and hypochromic with respect to the model aromatic compounds, and this is consistent with intensity borrowing. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5488–5503, 2004     

Determination of the glass transition temperature in thin polymeric films used for microelectronic packaging by temperature-dependent spectroscopic ellipsometry

We characterized the glass transition temperature T_g of thin polyimide films by temperature-dependent spectroscopic ellipsometry and compared the results to DSC measurements of the bulk polymer. The effect of the curing temperature on T_g and the thermal expansion α(T) was analyzed. An improved ellipsometric data evaluation was used to get most precise and reliable T_g data. T_g increased with increasing curing temperature, while the bulk T_g was considerably lower than the thin film T_g. Both observations are attributed to the temperature sensitive release of the imidization by-product 2-hydroxyethyl methacrylate (HEMA) and crosslinker components as well as decomposition products from the material. Variation in the curing temperatures of 230–380 °C led to an increase in the T_g of 34 °C.     

Group contribution method for the swelling behavior of thermo‐responsive hydrogels

A group contribution method is introduced to describe the swelling behavior of thermo‐sensitive hydrogel systems. The accuracy of group contribution calculations is strongly dependent on the choice of thermodynamic model. Therefore, we revise the modified double lattice (MDL) model and develop a new expression for the interaction energy parameter using the association theory of Sanchez to take into account complex polymer/solvent mixing. The net Helmholtz energy for a hydrogel is established by combining the revised MDL model and modified Flory–Rehner elastic model. Group parameters are generated by fitting to experimental swelling data from both homopolymer and copolymer gel systems. The effect of salt on the volume phase transition is modeled by introducing an additional salt‐specific parameter to investigate various stimuli‐response swelling behavior. Calculated swelling equilibria using the new group contribution method shows excellent agreement with experimental data and various stimuli‐response volume phase transitions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 455–463     

Modeling of swelling by the fast transient fluorescence technique in a polymeric gel

The time‐resolved, fast transient fluorescence technique, which uses a strobe master system, was employed for studying the swelling of a disc‐shaped poly(methyl methacrylate) gel. The disc‐shaped gel was prepared by free‐radical copolymerization of methyl methacrylate and ethylene glycol dimethacrylate. Pyrene (Py) was introduced as a fluorescence probe during polymerization. After this gel was dried, swelling and slow‐release experiments were performed in chloroform at room temperature. Lifetimes of Py were measured during in situ swelling and slow‐release experiments. An equation was derived for low‐quenching efficiencies to interpret the behavior of lifetimes in and out of the gel during swelling. Py lifetimes in the gel decreased as swelling proceeded, but Py lifetimes out of the gel stayed constant during the slow‐release experiments. The Li–Tanaka equation was used to determine the cooperative and mutual diffusion coefficients, which were around 10⁻⁵ and 10⁻⁷ cm²s⁻¹, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 739–746, 2000     

Electrochemical, pulsed-field-gradient spin-echo NMR spectroscopic, and ESR spectroscopic study of the diffusivity of molecular probes inside gel-type cross-linked polymers

The permeability of five gel-type synthetic resins, obtained by polymerization of 1-vinylpyrrolidin-2-one cross-linked with N,N'-methylenebisacrylamide (1, 2, 3, 4, and 5 wt %) and swollen by N,N-dimethylformamide (DMF), has been analyzed. The diffusion of 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxyl (TEMPONE) was studied by ultramicroelectrode voltammetry. Similar measurements were performed for solutions of non-cross-linked poly(vinylpyrrolidone) in DMF. To provide information on the rotational mobility of TEMPONE and the translational mobility of DMF, electron spin resonance (ESR) spectroscopic and pulsed-field-gradient spin-echo nuclear magnetic resonance (PGSE-NMR) spectroscopic experiments, respectively, were carried out. Comparative analysis of the results obtained by electrochemical, ESR spectroscopic, and PGSE-NMR spectroscopic measurements showed that diffusivity inside the polymer framework is significantly affected by the extent of cross-linking, the size of the diffusing probe, and the presence of electrolytes.     

Preparation of carboxymethyl cellulose‐g‐poly (acrylamide)/montmorillonite superabsorbent composite as a slow‐release urea fertilizer

A superabsorbent composite was synthesized through free‐radical graft copolymerization of carboxymethyl cellulose, acrylamide, and montmorillonite by means of a crosslinker such as N,N′‐methylenebisacrylamide and potassium persulfate as an initiator. The preparation mechanism was proposed, and the composite structures were confirmed by using Fourier transform infrared spectroscopy, X‐ray diffraction, thermal gravimetric analysis, and scanning electron microscope. The factors influencing the swelling capacity of the composite were determined to accomplish the highly swelling capacity. The composition (15 wt% carboxymethyl cellulose, 5.4 wt% montmorillonite, 82 wt% acrylamide, 0.07 wt% N,N′‐methylenebisacrylamide, and 1.1 wt% potassium persulfate) exhibited high swelling capacity; it was selected to be loaded with urea fertilizer, and the release was investigated by measuring the conductivity. The results showed that the new controlled release system has good slow release properties.