Dependence of shrinking kinetics of poly(N-isopropylacrylamide) gels on preparation temperature

Preparation temperature dependence of equilibrium swelling degree and shrinking kinetics of poly(N-isopropylacrylamide) gel has been investigated by optical microscopic measurements. The degree of swelling, d/d₀, at 20 °C was found to be strongly dependent on the preparation temperature, T_prep, where d and d₀ are the diameter of gel during observation and preparation, respectively. The value of d/d₀ was about 1.2 for T_prep=20 °C, but steeply increased by approaching the phase separation temperature ≈32.0 °C. Above 32.0 °C, d/d₀ decreases stepwise to 1.46. This upturn in d/d₀ was correlated with spatial inhomogeneities in gels. That is, the gel became opaque by increasing T_prep. Though the shrinking half-time, t_1/2, of gel was on the order of 500 min for T_prep≤20 °C, t_1/2 decreased to 2 min for T_prep≥26 °C. Hence, a rapid shrinking was attained by simply increasing T_prep. The physical implication of this rapid shrinking in gels was discussed in conjunction with the gel inhomogeneities and a thermodynamic theory of swelling equilibrium.     

Super porous organic-inorganic poly(N-isopropylacrylamide)-based hydrogel with a very fast temperature response

Porous organic-inorganic (O-I) hydrogels showing a very fast temperature response, including very fast reswelling were prepared: only 6 s are needed for 72% deswelling (gel collapse) as well as for 72% reswelling. Both deswelling and reswelling are practically complete in 14 s. The gels were prepared from N-isopropylacrylamide (NIPA), N,N′-methylenebisacrylamide (BAA) and tetramethoxysilane (TMOS) by simultaneous radical polymerization and hydrolytic polycondensation of TMOS. The syntheses were carried out at temperatures below the lower critical solution temperature (LCST) of poly(NIPA) in two steps: during the first stage the temperature was held at T = +15 °C and during the second the temperature was lowered below the freezing point of the reaction mixture, T = −18 °C. The ice crystals, which grew during the second stage, served as the pore-forming agent. The best samples were obtained if the second stage was started shortly before the gel point of the reaction mixture. The introduction of the inorganic phase (silica) is necessary for the ability of fast reswelling and also results in a strong improvement of the hydrogels' mechanical properties, while the maximum swelling degree remains nearly unaffected.     

Preparation of macroporous poly(acrylamide) hydrogels in DMSO/water mixture at subzero temperatures

The copolymerization reactions of acrylamide and N,N’-methylenebis(acrylamide) were carried out in DMSO/water mixture (1:1 by volume) at various temperatures T_prep between -18 and 22 °C. Scanning electron microscopy analysis of the networks revealed the presence of porous morphologies. All the network samples formed at or below 0 °C have relatively small pores with sizes about 10⁰ μm. In this range of T_prep, the pore size only slightly increases with the temperature. As the temperature is increased above 0 °C, both the average pore size and the degree of polydispersity of the pores rapidly increase. Between T_prep=0 and 13 °C, the microstructure gradually changes from networks having relatively small pores to those exhibiting regular assembly of polyhedral large pores of about 10¹ μm in sizes. The formation of the porous structure at or below 0 °C is as a result of the cooling-induced phase separation mechanism, while the large polyhedral pores in the networks prepared at higher temperatures form during the freeze-dry process of the hydrogels after preparation.     

Rapid swelling and deswelling of thermoreversible hydrophobically modified poly(N-isopropylacrylamide) hydrogels prepared by freezing polymerisation

Rapid response thermally sensitive hydrophobically modified poly(N-isopropylacrylamide) hydrogels have been synthesised successfully using a two-step polymerisation method, the initial polymerisation being carried out at 20 °C, followed by polymerisation at −28 °C for 24 h. The results show that the swelling/deswelling rates of poly[N-isopropylacrylamide-co-(di-n-propylacrylamide)] P(NIPA-co-DPAM) hydrogels prepared by two-step polymerisation are much faster than for the same type of hydrogels prepared via conventional methods (30 °C for 24 h), i.e. the time for the former xerogel to absorb 70 and 90 wt% is just 30 and 240 min, respectively, compared to the latter xerogel which takes 1600 and 2500 min to absorb the same amounts of water. During deswelling (shrinking), the hydrogel loses 95 wt% water in 1 min, compared to a timescale for the corresponding cross-linked copolymers prepared by conventional methods of about 5 h for 50 wt% water loss. Scanning electron microscopy, and flotation experiments together with swelling ratio studies reveal that the polymeric network of the former hydrogel is characterised by an open structure with more pores and higher swelling ratio but lower mechanical strength compared to the latter hydrogels. Such rapid response hydrogels have potential applications in separation and drug release technologies for example.     

Freezing as a path to build macroporous structures: Superfast responsive polyacrylamide hydrogels

Macroporous polyacrylamide (PAAm) hydrogels were prepared from acrylamide monomer and N,N′-methylene(bis)acrylamide (BAAm) crosslinker in frozen aqueous solutions. It was found that the swelling properties and the elastic behavior of the hydrogels drastically change at a gel preparation temperature of −6 °C. The hydrogels prepared below −6 °C exhibit a heterogeneous morphology consisting of pores of sizes 10–70 μm, while those formed at higher temperatures have a non-porous structure. PAAm networks with largest pores were obtained at −18 °C. The pore size of the networks increased while the thickness of the pore walls decreased by decreasing the monomer concentration. The hydrogels formed below −6 °C exhibit superfast swelling and deswelling properties as well as reversible swelling–deswelling cycles in water and in acetone, respectively.     

Strain recovery of post-yield compressed semicrystalline poly(butylene terephthalate)

Cubic specimens of a semicrystalline poly(butylene terephthalate) (PBT) have been compressed up to post-yield deformation levels with a fast (3.0 × 10⁻² s⁻¹) and a slow (1.5 × 10⁻⁴ s⁻¹) strain rate at three different temperatures (25 °C, 45 °C, and 100 °C, i.e. below, close and above the glass transition temperature of the material, T_g, respectively). Differently from literature results reported for amorphous polymers, semicrystalline PBT shows that, after a post-yield deformation, recovery occurs also at temperatures higher than T_g, and that an irreversible deformation, ?_irr, is set in the material. The irreversible strain component has been evaluated as the residual deformation after a thermal treatment of 1 h at 180 °C.After unloading, isothermal strain recovery has been monitored for time periods of 1 h at various temperatures. From the obtained data, strain recovery master curves have been constructed by a time-temperature superposition scheme. The features of the recovery process for the various deformation conditions have been analysed. In particular, it appears that specimens deformed below T_g show a lower irreversible component, whereas, when deformed above T_g, they display a higher irreversible deformation and a slower recovery process. Moreover, the effect of deformation rate appears particularly marked for samples deformed above T_g.     

Synthesis and aqueous solution characterization of amphiphilic diblock copolymers containing carbazole

A series of near-monodisperse diblock copolymers of 2-(N-carbazolyl)ethyl methacrylate and 2-(dimethylamino)ethyl methacrylate (DMAEMA) of relatively low molecular weights (2600-24,000 g mol⁻¹) were synthesized by group transfer polymerization using tetrahydrofuran (THF) as a solvent. The molecular weight distributions and compositions of all the copolymers were obtained using gel permeation chromatography (GPC) in THF and proton nuclear magnetic resonance (¹H NMR) spectroscopy, respectively. Differential scanning calorimetry and thermal gravimetric analysis provided low glass transition temperatures (T_gs) of about 60 °C and decomposition temperatures between 320 and 450 °C for the copolymers, respectively. The three copolymers with the highest DMAEMA content were water-soluble below pH 7. Aqueous GPC at pH 3 showed that the water-soluble block copolymers formed micelles with apparent number average molecular weights above 100,000 g mol⁻¹.     

Synthesis, characterization and optical properties of cross-linkable poly(phthalazinone ether ketone sulfone)

Cross-linkable poly(phthalazinone ether ketone sulfone) bearing tetrafluorostyrene groups (PPEKS-FSt) has been prepared by copolycondensation reaction for optical waveguide applications. The resulting amorphous polymer exhibits good solubility in some common polar organic solvents (e.g., N,N′-dimethylacetamide, N-methyl-2-pyrrolidinone, chloroform) at room temperature, and can be easily spin-coated into thin films with good optical quality. The glass transition temperature (T_g) and the temperature of 1% weight loss (1% T_d) are 261 °C and 494 °C, respectively, which could be further increased by 31 °C and 14 °C upon thermal cross-linking. The cross-linked polymer thin films exhibit high refractive index (∼1.65, TE mode), high thermo-optic coefficient value (dn/dT) (−1.455 × 10⁻⁴/°C, TE mode), low optical loss (less than 0.24 dB/cm at 1310 nm) and relatively low birefringence (∼0.007).     

Temperature dependence of density of polymer gels: Effects of ionizable groups in copoly(N-isopropylacrylamide/acrylic acid or sodium acrylate)-water systems

Effects of ionizable groups in hydrogels of copolymer networks on the volumetric contraction-expansion process were investigated. Polymer networks used were: copoly[N-isopropylacrylamide (NIPA)(1 − x)/acrylic acid (HAc) or sodium acrylate (NaAc)(x)] with mole fraction of minor component (x) assuming 0.0114 and 0.0457. From the temperature (T) dependence of total volume of gels, densities of the polymer and solvent (water) components, and stoichiometry, we evaluated (1) the volume of gels occupied by a single mean polymeric residue and associated water molecules (expressed in units of nm³), mean v_sp(gel), and (2) number of water molecules per single mean polymeric residue, mean N_s(gel), from near 273 K to 323 K. These quantities (1) and (2) listed above showed how acid and salt forms affect differently on volumetric changes of gels over 50 K. We developed an approach to evaluate volumetric changes of gels solely caused by a single polymeric residue of a minor component (x < 0.05) plus associated water by applying thermodynamic first-order perturbation theory. They are specific v_sp(gel)(T) for a single HAc or NaAc polymeric residue plus associated water and the corresponding specific N_s(gel)(T). Specific v_sp(gel)(HAc or NaAc)(T) and the corresponding specific N_s(gel(T)) revealed specific characteristics in thermal behavior near their respective transition temperatures from the swollen to shrunken states. We found these thermal changes shown at the nano-scale match very well with specific changes in the molality(T) of both ionizable groups. In fact, these are directly triggered by varying contents of water in gels. Based on the understanding of dissociative equilibrium attained by ionizable groups, we successfully replaced Na⁺ in hydrogels of copoly[NIPA(1 − x)/NaAc(x)] (x = 0.0457) by hydrogen ions. Absence of Na⁺ in treated hydrogels was experimentally verified by ²³Na NMR and Na atomic absorption flame photometry. Discontinuity in the volumetric contraction-expansion process from the swollen to shrunken states and vice versa was not observed in contradiction to the previous reports [Hirotsu S, Hirokawa Y, Tanaka T. J Chem Phys 1987;87:1392-5. Matsuo SE, Tanaka T. J Chem Phys 1988;89:1695-703.] obtained by the conventional swelling experiments.     

Temperature sensitive poly(N-t-butylacrylamide-co-acrylamide) hydrogels: synthesis and swelling behavior

A series of temperature sensitive hydrogels was prepared by free-radical crosslinking copolymerization of N-t-butylacrylamide (TBA) and acrylamide in methanol. N,N′-methylenebis(acrylamide) was used as the crosslinker. It was shown that the swelling behavior of the hydrogels can be controlled by changing the amount of TBA units in the network chains. Hydrogels immersed in dimethylsulfoxide (DMSO)-water mixtures exhibited reentrant swelling behavior, in which the gels first deswell then reswell if the DMSO content of the solvent mixture is continuously increased. In water over the temperature range of 2-64 °C, hydrogels with less than 40[percnt] TBA by mole were in a swollen state while those with TBA contents higher than 60[percnt] were in a collapsed state. Hydrogels with 40-60[percnt] TBA exhibited swelling-deswelling transition in water depending on the temperature. The temperature interval for the deswelling transition of 60[percnt] TBA gel was found to be in the range from 10 to 28 °C, while for the 40[percnt] TBA gel, the deswelling started at about 20 °C and continued until the onset of the hydrolysis of the network chains at around 64 °C. It was shown that the Flory-Rehner theory of swelling equilibrium provides a satisfactory agreement to the experimental swelling data of the hydrogels, provided that the sensitive dependence of the χ parameter on both temperature and polymer concentration is taken into account.     

Thermoreversible swelling behaviour of hydrogels based on N-isopropylacrylamide with a hydrophobic comonomer

Hydrogels were prepared by free radical polymerisation in aqueous solution of N-isopropylacrylamide (NIPA) and of NIPA with di-n-propylacrylamide (DPAM), di-n-octylacrylamide (DOAM) or di-dodecylacrylamide (DDAM) as hydrophobic comonomer. N,N-methylene bisacrylamide (BIS) and glyoxal bis(diallyacetal) (GLY) were used as crosslinkers. A series of copolymers with three different comonomer contents was synthesised and for some polymers three different crosslinker concentrations were employed. The swelling equilibrium of these hydrogels was studied as a function of temperature, hydrophobic comonomer species and content in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS). In pure water the gels showed a discontinuous volume phase transition at 33 and 30 °C for PNIPA and hydrophobically modified PNIPA copolymeric hydrogels, respectively. The swelling ratio r and the transition temperature (LCST) increased at low temperatures with the addition of SDS, this is ascribed to the conversion of non-ionic PNIPA gels into polyelectrolyte gels through the binding of SDS. At SDS concentration below 0.5 wt%, gels exhibited a single discontinuous volume transition at 36-38 °C. However, for SDS concentration above 0.5 wt%, two discontinuous volume transitions at 36-40 and 70 °C were observed. Additionally, the replacement of BIS by the novel octafunctional crosslinker glyoxal bis(diallylacetal) (GLY) yielded an increase in the swelling ratio.     

Swelling–deswelling kinetics of poly(N‐isopropylacrylamide) hydrogels formed in PEG solutions

A series of poly(N‐isopropylacrylamide) (PNIPA) hydrogels was prepared by free‐radical crosslinking copolymerization of N‐isopropylacrylamide (NIPA) and N,N′‐methylenebisacrylamide (BAAm) in aqueous solutions of poly(ethylene glycol) of molecular weight 300 g/mol (PEG). The amount of PEG in the polymerization solvent, the crosslinker (BAAm) content, and the gel preparation temperature (T_prep) were varied in the gelation experiments. The hydrogels were characterized by the equilibrium swelling and elasticity tests as well as by the measurements of the deswelling–reswelling kinetics of the hydrogels in response to a temperature change between 25 and 48°C. The rate of deswelling of the swollen gel increases while the rate of reswelling of the collapsed gel decreases as the amount of PEG in the polymerization solvent is increased or as the crosslinker content is decreased. The T_prep effect on the swelling kinetics of the hydrogels was only observed if the PEG content of the polymerization solvent is less than 20%, which is explained with the screening of H‐bonding interactions in concentrated PEG solution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 37–44, 2006     

Novel thermo-responsive membranes composed of interpenetrated polymer networks of alginate-Ca and poly(N-isopropylacrylamide)

In this work, interpenetrated polymer networks (IPN) composed of alginate-Ca²⁺ and poly(N-isopropylacrylamide), PNIPAAm, were synthesized and their water uptake capability was measured at temperatures from 25 to 40 °C and compared to that of pure alginate-Ca²⁺ hydrogels without PNIPAAm. A sharp decrease of WU was observed when IPN hydrogels are heated above 32-33 °C. The phenomenon is associated to a drastic shrinking of hydrogels. At temperatures above 32 °C the PNIPAAm chains collapse, contracting their network and pulling back the alginate-Ca²⁺ network. The rate of shrinking depends of the heating rate. The phenomenon is more effective and faster in IPN containing lower amount of alginate-Ca²⁺. The shrunken IPN hydrogels can be re-swollen but the expansion is slower than the shrinking. The diffusion of Orange II dye through the membrane of IPN hydrogels decreases if the temperature is raised up to 35 °C. The shrinking results in a decrease of the average pores size that makes more difficult the diffusion of Orange II. The average pore size was evaluated in several stages by analysis of SEM micrographs of freeze dried samples: 102.0±14.3 μm at 25 °C, 15.7±5.4 μm at 33 °C and 0.4±0.3 μm at 40 °C. Below the LCST of PNIPAAm, the IPN hydrogels exhibit a morphology characterized by open pores but above the LCST their surface becomes more regular and compact. As a consequence, an increase of the apparent activation energy for permeability, , of Orange II is measured.     

Copolymer hydrogels based on N-isopropylacrylamide and itaconic acid

In this study, the swelling behaviour of copolymer hydrogels of N-isopropylacrylamide (NIPAM) and itaconic acid (IA) in response to temperature and pH value of the external media was studied. The equilibrium degree of swelling for PNIPAM and PNIPAM/IA copolymers was greater at 25 °C than at 37 °C. The degree of swelling was low at low pH values. As the degree of ionization increased above the nominal pK_a values of IA, the increased hydrophilicity resulted in larger degrees of swelling. At 37 °C, the PNIPAM hydrogel and some copolymers show anomalous swelling behaviour, i.e. the overshooting effect, in buffered solutions of certain pH values. A swelling-deswelling study showed that the deswelling process of the hydrogels was faster then the swelling process. According to dynamic swelling studies, the diffusion exponent and the diffusion coefficient both increase with increasing content of IA.     

DSC, dielectric and dynamic mechanical behavior of two- and three-component ordered polyurethanes

Liquid crystalline (LC) polyurethanes were made from two diisocyanates (flexible HMDI and stiff TDI) (DIs), mesogenic diol (D) and a polybutadiene-diol (B) with stoichiometric ratios of reactive hydroxy (OH) and isocyanate (NCO) groups ((NCO)_DI/((OH)_D+(OH)_B)=1/1). Two- (B/DIs, D/DIs) and three-component ((D+B)/DIs, D/B=1/1 by weight) polymers were prepared and their dielectric, dynamic mechanical and DSC behavior was investigated. For neat B, the glass transition temperature T_gB (∼−46 °C) was detected. Two-component B/HMDI and B/TDI polymers have exhibited a homogeneous structure with the glass transition temperatures T_gU∼−9 and 2 °C. On the other hand, for D/DI polymers on cooling from the melt and subsequent heating the glass transitions at T_gU∼41 °C (D/HMDI) and 58 °C (D/TDI) together with nematic and smectic mesophases were found. In three-component systems, additional glass transitions at T_gB∼−41 °C (B/D/HMDI) and −31 °C (B/D/TDI) were observed. This means that the polymers exhibit a distinct two-phase structure with soft polybutadiene (B) and hard polyurethane (D/DI) phases. In hard polyurethane phase, the glass transitions at T_gU and LC mesophases similar to those found in two-component D/DI polyurethanes were detected. Dielectric and dynamic mechanical results correlate well with DSC measurements.     

Synthesis of spherical shape borate-based bioactive glass powders prepared by ultrasonic spray pyrolysis

Spherical shape borate-based bioactive glass powders with fine size were directly prepared by high temperature spray pyrolysis. The powders prepared at temperatures between 1200 and 1400 °C had mixed phase with small amounts of fine crystal and an amorphous rich phase. Glass powders with amorphous phase were prepared at a temperature of 1500 °C. The mean size of the glass powders prepared by spray pyrolysis was 0.76 μm. The glass powders prepared at a temperature of 1200 °C had two distinct exothermic peaks (T_c1 and T_c2) at temperatures of 588 and 695 °C indicating crystallization. The glass transition temperature (T_g) of the powders prepared at a temperature of 1200 °C was 480 °C. Phase-separated crystalline phases with spherical shape were observed from the surface of the pellet sintered at a temperature of 550 °C. Crystallization of the pellet was completely occurred at temperatures of 750 and 800 °C. The pellets sintered at temperatures below 700 °C had single crystalline phase of CaNa₃B₅O₁₀. The pellet sintered at a temperature of 800 °C had two crystalline phases of CaNa₃B₅O₁₀ and CaB₂O₄.     

Characterisation of activated nanoporous carbon for supercapacitor electrode materials

Commercial nanoporous carbon RP-20 was activated with water vapor in the temperature range from 950 °C to 1150 °C. The XRD analysis was carried out on nanoporous carbon powder samples to investigate the structural changes (graphitisation) in modified carbon that occurred at activation temperatures T ? 1150 °C. The first-order Raman spectra showed the absorption peak at 1582 cm⁻¹ and the disorder (D) peak at 1350 cm⁻¹. The low-temperature N₂ adsorption experiments were performed at −196 °C and a specific surface area up to 2240 m²g⁻¹ for carbon activated at T = 1050 °C was measured. The cell capacitance for two electrode activated nanoporous carbon system advanced up to 60 F g⁻¹ giving the specific capacitance ∼240 F g⁻¹ to one electrode nanoporous carbon ∣1.2 M (C₂H₅)₃CH₃NBF₄ + acetonitrile solution interface. A very wide region of ideal polarisability for two electrode system (∼3.2 V) was achieved. The low frequency limiting specific capacitance very weakly increases with the rise of specific area explained by the mass transfer limitations in the nanoporous carbon electrodes. The electrochemical characteristics obtained show that some of these materials under discussion can be used for compilation of high energy density and power density non-aqueous electrolyte supercapacitors with higher power densities than aqueous supercapacitors.     

Immobilization of polyvinylacetate macromolecules on hydroxyapatite nanoparticles

Concentration dependence of the storage modulus, E′, was investigated for polyvinylacetate (PVAc) filled with hydroxyapatite (HAP) nanoparticles. The filler volume fraction, v_f, varied from 0 to 0.05 and the E′ and loss tangent, tan δ, were measured below neat matrix T_g at −40 °C and above neat matrix T_g at +50 °C at 1 Hz. The T_g determined as the position of the maximum on the temperature dependence of tan δ increased by 14 °C compared to the neat PVAc (39 °C) by adding 5 vol.% of HAP. At −40 °C, the observed small increase of E′ with v_f was in agreement with the prediction based on the simple Kerner equation. At +50 °C, the increase of E′ with v_f observed was an order of magnitude greater than that predicted using the simple continuum mechanics model. An attempt was made to explain the observed deviation employing the hypothesis of immobilized entanglements.     

Synthesis, characterization and optical properties of fluorinated poly(aryl ether)s containing phthalazinone moieties

A series of novel fluorinated poly(aryl ether)s containing phthalazinone moieties (FPPEs) have been prepared by a modified synthetic procedure for optical waveguide applications. The obtained random copolymers exhibited excellent solubility in polar organic solvents, high glass transition temperatures (T_gs: 185-269 °C), good thermal stabilities (the temperatures of 1% weight loss: 487-510 °C) and good optical properties. By adjusting the feed ratio of the reactants, the refractive indices of TE and TM modes (at 1550 nm) could be well controlled in the range of 1.575-1.498 and 1.552-1.484, respectively. The optical losses of the FPPEs exhibited relatively low values (less than 0.27 dB/cm at 1310 nm). Additionally, the thermo-optic coefficient (dn/dT) values of the FPPEs at 1310 nm and 1550 nm (TE mode) ranged from −0.97 × 10⁻⁴ °C to −1.33 × 10⁻⁴ °C and from −0.96 × 10⁻⁴ °C to −1.29 × 10⁻⁴ °C, respectively.     

Unusual swelling behavior of polymer-clay nanocomposite hydrogels

The swelling behavior and the elastic properties of nanocomposite hydrogels have been investigated. The hydrogels were prepared by free-radical polymerization of the monomers acrylamide (AAm), N,N-dimethylacrylamide (DMA), and N-isopropylacrylamide (NIPA) in aqueous clay suspensions at 21 °C. Laponite with a radius of gyration in distilled water of 20 nm was used as clay particles in the hydrogel preparation. The reactions with AAm monomer were carried out in the presence of the chemical crosslinker N,N′-methylenebis(acrylamide) (BAAm). It was found that the volume of nanocomposite hydrogels immersed in water rapidly increases and attains a maximum value after about one day. Surprisingly, further increase in the swelling time results in the deswelling of the gels until they reach a limiting swelling ratio after about 5 days. This unusual swelling behavior is observable only when the clay concentration in the hydrogel is above the overlap threshold c^∗. Swelling measurements combined with the elasticity tests show that the effective crosslink density first decreases, but then increases with increasing time of swelling of the hydrogels. The results were explained in terms of the rearrangements of the highly entangled polymer chains and clay particles during the gel volume change.