Determination of the swelling behavior of superabsorbent polymers by a tracer-assisted on-line spectroscopic measurement

This work reports on a method for the accurate determination of kinetic swelling behavior and properties of superabsorbent polymers by a tracer-assisted on-line spectroscopic measurement. Based on monitoring the spectral absorption of a tracer compound (blue dextran 2000) at 610 nm in a superabsorbent polymer containing solution, the swelling (water absorption) of the polymer during the process can be followed, from which the parameters in a kinetic equation can be obtained. The results showed that the data obtained by the present method has a good measurement precision and accuracy, in which the relative differences were less than 4.0% when comparing the data measured by a reference method (i.e., the tea bag method). Since the present method can perform an on-line measurement, it is much superior to the current tea bag method and therefore is very suitable to be used in the process related study for the swelling behavior of superabsorbent polymers in many applications.     

Preparation and properties of diatomite composite superabsorbent

A novel diatomite composite superabsorbent was synthesized by solution polymerization of partially neutralized acrylic acid and diatomite, using N,N′-methylenebisacrylamide as a crosslinking agent and hydrogen peroxide and L -ascorbic acid as a redox initial system. The influences of some reaction conditions, such as diatomite content, neutralization degree of acrylic acid, amount of initiator, amount of crosslinking agent, monomer concentration, and the reaction temperature on swelling characteristic were investigated. The water absorbency of the sample prepared at optimum conditions was 99 g/g in 0.9 wt% NaCl solution. The results of swelling rate measurement showed that diatomite composite superabsorbent had better swelling rate than that of poly(sodium acrylate) prepared in the same conditions. Other properties, i.e. water retention, reswelling ability and resistance to salt, were also examined. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and Swelling Behaviors of P(AMPS-co-AAc) Superabsorbent Hydrogel Produced by Glow-Discharge Electrolysis Plasma

Highly swelling P(2-acrylamido-2-methyl-1-propanesulfonic acid- co-acrylic acid) (P(AMPS-co-AAc)) superabsorbent hydrogel was synthesized in aqueous solution by a simple one-step using glow-discharge electrolysis plasma technique, in which N,N’-methylenebisacrylamide was used as a crosslinking agent. The structure, thermal stability and morphology of P(AMPS-co-AAc) superabsorbent hydrogel were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. A mechanism for synthesis of P(AMPS-co-AAc) superabsorbent hydrogel was proposed. The reaction parameters affecting the equilibrium swelling (i.e., discharge voltage, discharge time, macroscopic temperature of the liquid phase, mass ratio of AMPS to AAc, and content of crosslinker) were systematically optimized to achieve a superabsorbent hydrogel with a maximum swelling capacity. The hydrogel formed which absorbed about 1,685 g H₂O/g dry hydrogel of the optimized product was used to study the influence of various pH values and salts solutions (NaCl, KCl, MgCl₂, and CaCl₂) on the equilibrium swelling. In addition, swelling kinetics in distilled water and on–off switching behavior were preliminarily investigated. The results showed that superabsorbent hydrogel was responsive to the pH and salts.     

Preparation and properties of superabsorbent containing starch and sodium humate

Starch and sodium humate were utilized as raw material for synthesizing starch‐g‐poly(acrylic acid)/sodium humate (St‐g‐PAA/SH) superabsorbent by graft copolymerization reaction of starch (St) and acrylic acid (AA) in the presence of sodium humate (SH) in aqueous solution. The effect of weight ratio of AA to St, initial monomer concentration, neutralization degree of AA, amount of crosslinker, initiator and SH on water absorbency of the superabsorbent were studied. The swelling rate and swelling behavior in NaCl solution as well as reswelling ability of the superabsorbent were systematically investigated. The results showed that the superabsorbent synthesized under optimal conditions with SH content of 7.7 wt% and St content of 11.5 wt% exhibits water absorbency of 1100 g/g in distilled water and 86 g/g in 0.9 wt% NaCl solution, respectively. Introducing SH into the St‐g‐PAA polymeric network can improved the swelling rate and reswelling capability of the superabsorbent. Copyright © 2008 John Wiley & Sons, Ltd.     

Study on superabsorbent composite—VII. Effects of organification of attapulgite on swelling behaviors of poly(acrylic acid‐co‐acrylamide)/sodium humate/organo‐attapulgite composite

A novel multifunctional superabsorbent composite from acrylic acid (AA), acrylamide (AM), sodium humate (SH) and organo‐attapulgite (organo‐APT), PAA‐AM/SH/organo‐APT, was synthesized by aqueous solution polymerization, using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The organification of APT with hexadecyltrimethyl ammonium bromide (HDTMABr) was proved by FT‐IR. The effects of organo‐APT (HDTMA‐APT) content in the superabsorbent composite and organification degree of it on water absorbency of the superabsorbent composite were studied. The effects of incorporated HDTMA‐APT on swelling rate, water absorbency in various saline solutions and reswelling capability of the superabsorbent composite were also investigated. The results indicate that organification of APT had a remarkable influence on swelling behaviors of the superabsorbent composites. Comparing with the composite doped with APT, water absorbency for the composite incorporated with 10 wt% HDTMA‐APT was enhanced from 996 to 1282 g g^?1 in distilled water and from 63 to 68 g g^?1 in 0.9 wt% NaCl solution, respectively. The superabsorbent composite acquired its highest water absorbency when the organification degree of APT was 8.02 wt%. Water absorbency of the composites in various saline solutions decreased with the increasing concentration, especially for the multivalent cations. In addition, swelling rate and reswelling capability of the superabsorbent composite were also improved by introducing HDTMA‐APT into the composite compared with that of incorporating APT. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation and swelling behavior of amphoteric superabsorbent composite with semi-IPN composed of poly(acrylic acid)/Ca-bentonite/poly(dimethyldiallylammonium chloride)

Amphoteric superabsorbent composite with semi-interpenetrating polymer networks (semi-IPN) composed of poly(acrylic acid) (PAA)/Ca-bentonite/poly(dimethyldiallylammonium chloride) (PDMDAAC) was prepared by a combination of intercalative polymerization and a sequential IPN method and the effects of reaction parameters on the swelling capacity were studied. PDMDAAC was used as a polycation to modify bentonite and form semi-IPN with lightly crosslinked PAA. FTIR and TG were used to characterize the amphoteric superabsorbent composites with semi-IPN. The thermal stability of the product was not degraded as in the case of using small molecular surfactant to modify bentonite. The contents of carboxylic groups and nitrogen had been determined. This indicated that the product with certain content of carboxylic groups and nitrogen is inclined to exhibit excellent swelling capacity. The presence of PDMDAAC improved the swelling capacity. The resulting amphoteric superabsorbent composite showed excellent swelling capacity of 1578 g/g in distilled water and 136 g/g in 0.9 wt% NaCl solution. Copyright © 2007 John Wiley & Sons, Ltd.     

Different types of microfibrillated cellulose as filler materials in polysodium acrylate superabsorbents

Three types of microfibrillated cellulose(MFC)with differences in structure and surface charge were used at low concentration as filler materials in polysodium acrylate superabsorbents(SAPs).The swelling of the composite hydrogels was determined in 0.9%NaCl solution as well as in deionized water.The shear modulus of the samples was determined through uniaxial compression analysis after synthesis and after swelling in 0.9%NaCl solution.Furthermore,the ability to retain filler effects after washing was investigated.The results showed that all of the investigated MFCs had a strong reinforcing effect on the shear modulus after synthesis.The filler effect on swelling and on the associated shear modulus of swollen samples showed a more complicated dependence on structure and surface charge.Finally,it was found that the filler effects were reasonably retained after washing and subsequent drying.The results confirm that MFC holds great potential as a filler material in superabsorbent applications.Furthermore,the results provide some insight on how the structural properties and surface charge of MFC will affect gel properties depending on swelling conditions.This information should be useful in evaluating the use of different types of MFC in future applications.     

Kinetic models of sorption: a theoretical analysis

The kinetics of sorption from a solution onto an adsorbent has been explored theoretically. The general analytical solution was obtained for two cases. It has been shown that at high initial concentration of solute (sorbate) the general equation converts to a pseudo-first-order model and at lower initial concentration of solute it converts to a pseudo-second-order model. In other words, the sorption process obeys pseudo-first-order kinetics at high initial concentration of solute, while it obeys pseudo-second-order kinetics model at lower initial concentration of solute. The theoretical results (derived equations) show that the observed rate constants of pseudo-first-order and pseudo-second-order models are combinations of adsorption and desorption rate constants and also initial concentration of solute. The obtained theoretical equations are used to correlate experimental data for sorption kinetics of some solutes on various sorbents. The predictions of the theory are in excellent agreement with the experimental data.     

A Novel Superabsorbent Composite Based on Poly(Aspartic Acid) and Organo-Kaolin

A novel superabsorbent composite of poly(aspartic acid)(PAsp)/organo-kaolin was prepared by the nonaqueous inverse-phase suspension method and characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The equilibrium swelling ratio of the composite could be effectively improved by the introduction of organo-kaolin and when the organo-kaolin content is 3?wt% the maxima were achieved, 753 for distilled water and 125 for 0.9?wt% NaCl aq. solution. Salt resistance, pH sensibility and temperature response were also studied considering the practical application of the PAsp/organo-kaolin superabsorbent composite.     

Modified carrageenan. 5. Preparation,swelling behavior,salt‐ and pH‐sensitivity of partially hydrolyzed crosslinked carrageenan‐graft‐polymethacrylamide superabsorbent hydrogel

The polysaccharide, kappa‐carrageenan (κC) was chemically modified to achieve a novel superabsorbent hydrogel via graft copolymerization of methacrylamide (MAM) onto the substrate followed by alkaline hydrolysis. Ammonium persulfate (APS) and N,N′‐methylene bisacrylamide (MBA) were used as a free‐radical initiator and a crosslinker, respectively. The saponification reaction was carried out using sodium hydroxide aqueous solution. Either κC‐g‐PMAM or hydrolyzed κC‐g‐PMAM (PMAM: polymethacrylamide) was characterized by FT‐IR spectroscopy. The effect of grafting variables (i.e. concentration of MBA, MAM, and APS) and alkaline hydrolysis conditions (i.e. NaOH concentration, hydrolysis time and temperature) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. The swelling capacity of these hydrogels was also measured in various salt solutions. Results indicated that the swelling ratios decreased with an increase in the ionic strength of the salt solutions. This behavior can be attributed to charge screening effect for monovalent cations, as well as ionic crosslinking for multivalent cations. Absorbency of superabsorbing hydrogels was examined in buffer solutions with pH range 1–13. Also, the pH reversibility and on–off switching behavior, at pH values 3.0 and 8.0, makes the synthesized hydrogels good candidates for controlled delivery of bioactive agents. Finally, swelling kinetics in distilled water and various salt solutions was preliminary investigated. Results showed that the swelling in water was faster than in saline solutions. Copyright © 2004 John Wiley & Sons, Ltd.     

粉煤灰复合聚丙烯酸钠凝胶的制备及其溶胀性能

粉煤灰(CFA)存在的情况下,采用自由基溶液聚合法,以过硫酸钾(KPS)为引发剂,N,N'-亚甲基双丙烯酰胺(NNMBA)为交联剂,制备了粉煤灰复合聚丙烯酸钠凝胶(CFAPAANa)。 以丙烯酸单体质量为基准,当交联剂用量为0.08%,引发剂用量为0.4%,粉煤灰用量为3%,丙烯酸中和度为70%,聚合温度为70 ℃时,所合成的粉煤灰复合聚丙烯酸钠凝胶在蒸馏水和生理盐水中平衡溶胀比最高,分别为1556(g/g)和168(g/g)。 考察了复合凝胶在不同介质溶液中的溶胀动力学,保水性能以及在土壤中的降解行为。 溶胀动力学研究表明,蒸馏水中溶胀初期复合凝胶聚合物链段的扩散运动能够调控凝胶溶胀的快慢及程度,而生理盐水中水分子的平移和对流运动在凝胶的溶胀过程中起着关键性作用。 保水和降解实验结果表明,25 ℃时,50 h凝胶保水率为64%,土壤中50 d时降解率达60%。 相比于聚丙烯酸钠凝胶,粉煤灰复合凝胶保水率提高了8%。     

Radiation synthesis of superabsorbent poly(acrylic acid)–carrageenan hydrogels

A series of superabsorbent hydrogels were prepared from carrageenan and partially neutralized acrylic acid by gamma irradiation at room temperature. The gel fraction, swelling kinetics and the equilibrium degree of swelling (EDS) of the hydrogels were studied. It was found that the incorporation of even 1% carrageenan (sodium salt) increases the EDS of the hydrogels from 320 to 800 g/g. Thermal analysis were carried out to determine the amount of free water and bound water in the hydrogels. Under optimum conditions, poly(acrylic acid)–carrageenan hydrogels with high gel fraction (80%) and very high EDS (800 g/g) were prepared gamma radiolytically from aqueous solution containing 15% partially neutralized acrylic acid and 1–5% carrageenan. The hydrogels were also found to be sensitive to the pH and the ionic strength of the medium.     

Observation of single metal nanoparticle collisions by open circuit (mixed) potential changes at an ultramicroelectrode

Single nanoparticle (NP) collisions were successfully observed by a potentiometric measurement. The open circuit potential (OCP) of a measuring Au ultramicroelectrode (UME) changes when Pt NPs collide with the UME in a hydrazine solution. The OCP change is related to the redox processes, the concentration of particles, particle size, and electrode size. Compared with the amperometric technique, this approach has several advantages: higher sensitivity, simpler apparatus, fewer problems with NP decomposition, and contamination.     

Temperature Sensitive Superabsorbent Hydrogels from Poly(N-t-butyl acrylamide-co-acrylamide) Grafted on Sodium Alginate

Temperature-sensitive hydrogels based on N-t-butylacrylamide (TBA), acrylamide (AAm), and sodium alginate were prepared by free radical polymerization method. Methylenebisacrylamide (MBA) and amonium persulfate (APS) were applied as water soluble crosslinker and initiator, respectively. The chemical structure of the hydrogels was confirmed by FT-IR spectroscopy and thermogravimetric analysis (TGA) methods. Morphology of the samples was examined by scanning electron microscopy (SEM). By changing the initial TBA/AAm mole ratios, hydrogels with different swelling properties were obtained. The rate parameters were found to be 2.0, 2.4, and 3.5 min for the superabsorbents with AAm/TBA weight ratio of 1.0, 1.3 and 2.0 respectively. The swelling behavior in distilled water and different pH solutions was investigated. A preliminary swelling kinetics and the absorbency under load (AUL) were also studied. At the applied pressure (2.07 kPa), maximum swelling was found to be 17, 19, and 21 (g/g) for the superabsorbent hydrogels with AAm/TBA weight ratios of 1.0, 1.5 and 2.0, respectively.     

Modified chitosan III,superabsorbency, salt‐ and pH‐sensitivity of smart ampholytic hydrogels from chitosan‐g‐PAN

Polyacrylonitrile (PAN) grafted chitosan was prepared by ceric‐initiated graft polymerization of acrylonitrile onto chitosan in a homogenous medium. The copolymer chitosan‐g‐PAN product was then hydrolyzed to yield a novel smart hydrogel (H‐chitoPAN) with superabsorbing properties. The influence of add‐on values as well as temperature and time of hydrolysis of the initial chitosan‐g‐PAN on swelling behavior of the hydrogel was evaluated in water and various salt solutions. The swelling kinetics of the superabsorbing hydrogel was studied as well. The hydrogels exhibited ampholytic and pH‐sensitivity characteristics. Several sharp swelling changes were observed in lieu of pH variations in a wide range (pH 2–13). The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. Superabsorbency, pH‐ and salt‐sensitivity of the chitosan‐based hydrogel was briefly compared with the classical starch‐based superabsorbent, H‐SPAN. The pH‐reversibility and on–off switching behavior of the intelligent H‐chitoPAN hydrogels makes them good candidates for considering as potential drug carries. Copyright © 2004 John Wiley & Sons, Ltd.     

Preparation and swelling properties of hydrolysis-resistant superabsorbent composite based on acrylic acid and sodium bentonite

Abstract

A novel hydrolysis-resistant superabsorbent composite was prepared via the solution polymerization based on acrylic acid (AA) and sodium bentonite (SBT) as monomers, tetraallylammonium bromine (TAAB) as crosslinker and ammonium persulfate (APS) as initiator. The mechanism of polymerization and the structure of the superabsorbent polymer (SAP) were studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (X-ray), and scanning electron microscopy (SEM). The reaction conditions such as different mass ratios of APS to AA, TAAB to AA, SBT to AA, neutralization degree of AA were optimized by orthogonal experiment, and the influence of each reaction condition on the capacity of water absorption at 150?°C was investigated via single-factor controlled experiment. The hydrolysis resistance and swelling kinetics of the SAP were studied in different solutions at 150?°C. Compared to traditional SAPs, the SAP synthesized with TAAB as crosslinker performed a more excellent hydrolysis resistance and water absorbency capacity at high temperatures. The water absorbency in distilled water or 0.1?mol L^?1 NaCl solution could reach 392.6 and 145.2?g g^?1at 150?°C, respectively. The SAP maintaining high swelling capacity in the pH range of 5–9 indicated its wide application values in the acidic or alkaline environment at high temperature. In addition, the SAP exhibited good reusability which could still retain about 73% of its initial water absorbency after reswelling six times at 150?°C.     

Superabsorbent nanocomposite and its properties

Starch-g-poly (AM-AMPS)/illite superabsorbent nanocomposite was synthesized by grafting copolymerization reaction of starch, acrylamide(AM) and 2-acrylamido-2- methyl propane sulfonic acid (APMS) in the presence of illite micropowder in deionized aqueous solution. The influence factors on water absorbency of the superabsorbent nanocoposite was optimized by single factor experiment. The synthesized superabsorbent nanocomposite exhibited the maximum water absorbency of 1320?g H₂O/g in deionized water and 142?g H₂O/g in 0.9?wt% sodium chloride (NaCl) solution. FTIR spectra confirmed that the grafting copolymerization between -OH groups on starch and monomers generated during the reaction. XRD analysis confirmed that crystal interlayer of illite was pulled open to 3.61?nm. TEM showed that illite slice layer randomly dispersed in the matrix of superabsorbent nanocomposite. The superabsorbent nanocomposite had a better thermal stability the corresponding superabsorbent material without illite by TGA and DSC analysis. The superabsorbent nanocomposite with excellent water absorbency and water retention could be especially useful in industry, agricultural, horticultural applications.     

Study on superabsorbent composite. III. Swelling behaviors of polyacrylamide/attapulgite composite based on acidified attapulgite and organo-attapulgite

A novel kind of salt-resistant superabsorbent composite, polyacrylamide/attapulgite, from acrylamide (AM) and attapulgite (APT) was prepared by free-radical aqueous polymerization, using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The organification of APT with hexadecyltrimethyl ammonium bromide (HDTMABr) was proved by FTIR and XRD. The effects of acidified APT (H⁺-APT), organo-APT (HDTMABr-APT) and the content of APT in the superabsorbent composite on the water absorbency and the initial swelling rate for the superabsorbent composite in distilled water and in various saline solutions were studied. The effects of incorporated HDTMABr-APT and H⁺-APT on the reswelling ability of the superabsorbent composites were investigated. The results indicate that the incorporation of APT had remarkable influence on the improvement of water absorbency and swelling rate of the composites. Comparing with the composite doped with H⁺-APT, the water absorbency for the composite doped with 10 wt% HDTMABr-APT was enhanced from 2140 g g⁻¹ to 2800 g g⁻¹ in distilled water and from 100 g g⁻¹ to 121 g g⁻¹ in 0.9 wt% NaCl solution, respectively. The water absorbency of the composites in various saline solutions decreased with the increasing concentration, especially for the multivalent cations. In addition, the reswelling ability of the superabsorbent composites is also improved evidently by adding a small amount of HDTMABr-APT into the composite, comparing with that of incorporated with H⁺-APT.     

Molecular-surface forces in binary solutions

A formula is deduced for the potential energy of a molecule of solute in a dilute solution of low concentration as a function of an interface distance. A procedure is suggested for the determination of this energy by using the measurement of the flow rate of the solution across a membrane under the action of a concentration gradient. The flow rate of the solution is measured by means of a radioactive tracer and related to the energy of solute molecules on the basis of the thermodynamics of irreversible steady processes. An example of such measurements is given; the applicability of the calculations is not quite clear due to possible effect of electro-osmosis.     

The effects of the specific adsorption of anion on the reactivity of the Ru(0001) surface towards CO adsorption and oxidation: in situ FTIRS studies

The dynamics of adsorption and oxidation of CO on Ru(0001) electrode in sulfuric acid solution have been studied using in situ FTIR spectroscopy under potential control and at open circuit, the latter at 20 and 55 degrees C. The in situ IR data show clearly that the bisulfate anion adsorbs on the Ru(0001) surface over the potential range from -200 mV to 350 mV (vs. Ag/AgCl) at 20 degrees C in the absence and presence of adsorbed CO; however, increasing the temperature to 55 degrees C and/or increasing the concentration of dissolved O(2) reduces the bisulfate adsorption. The formation of surface (hydro-) oxide at higher potentials replaces the bisulfate adsorbates. Both linear (CO(L)) and three-fold hollow bonded CO (CO(H)) adsorbates were produced following CO adsorption at Ru(0001) in H(2)SO(4), as was observed in our previous studies in HClO(4). However, the amount of adsorbed CO observed in H(2)SO(4) was ca. 10% less than that in HClO(4); in addition, the CO(L) and CO(H) frequencies were higher in H(2)SO(4), and the onset potential for CO(ads) oxidation 25 mV lower. These new results are interpreted in terms of a model in which the adsorbed bisulfate weakens the CO adlayer, allowing the active Ru oxide layer to form at lower potentials. Significantly different results were observed at open circuit in H(2)SO(4) compared both to the data under potential control and to our earlier data in HClO(4), and these observations were rationalized in terms of the adsorbed HSO(4)(-) anions (pre-adsorbed at -200 mV) inhibiting the oxidation of the surface at open circuit (after stepping from the initial potential of -200 mV), as the latter was no longer driven by the imposed electrochemical potential but via chemical oxidation by trace dissolved O(2). Results from experiments at open circuit at 55 degrees C and using oxygen-saturated H(2)SO(4) supported this model. The difference in Ru surface chemistry between imposed electrochemical control and chemical control has potential implications with respect to fuel cell electrocatalysis.