Positron annihilation studies on radiation‐crosslinked poly(N‐isopropylacrylamide) hydrogels

The temperature‐sensitive poly(N‐isopropylacrylamide) hydrogels, prepared by γ and electron‐beam (EB) irradiation, were studied using positron annihilation lifetime spectroscopy (PALS). The effect of water content in the hydrogel on the ortho‐positronium (o‐Ps) lifetime and intensity was investigated. The observed positronium lifetime suggests microstructural differences between γ‐ and EB‐synthesized hydrogels. The distribution in positronium lifetime indicates nonhomogeneity in the distribution of free‐volume holes in EB‐synthesized hydrogels. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3462–3466, 2000     

Positron annihilation properties of copolyimides and copolyamides with microphase‐separated structures

The positron annihilation lifetime (PAL) of a series of copolyimides and copolyamides with microphase‐separated structures was measured to investigate the effects of different hard‐segment polymers on the PAL properties of soft‐segment domains of poly(dimethyl‐siloxane) (PDMS) and poly(ethylene oxide) (PEO). The lifetime (τ₃) and intensity (I₃) of the long‐lived component are given as a function of the PDMS or PEO content for a series of copolymers, of which the density roughly obeys the additive rule except for the PDMS‐segmented copolyamides. The PDMS‐segmented copolyimides and copolyamides show much smaller I₃ values than those estimated from the additive rule. The lifetime distribution of the long‐lived component for the PDMS‐segmented copolyamides is composed of two components. The longer‐lifetime component is attributed to pure PDMS domains, and the shorter‐lifetime component is attributed to the polyamide domains, intermediate phases, and PDMS domains containing small amounts of short amide blocks. Despite the high PDMS content, the latter component is rather large. Thus, the positronium formation in the PDMS domains of the copolyimides and copolyamides is effectively reduced. This can be explained by the combination of the difference in the electron affinity of the PDMS and polyimide or polyamide segments and the incomplete phase separation. The PEO‐segmented copolyimides show much smaller I₃ values than those predicted from the additive rule. This is likely attributable to the effects of the intermediate phases. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1123–1132, 2000     

Semi‐interpenetrating polymer networks composed of poly(N‐isopropyl acrylamide) and polyacrylamide hydrogels

Three series of semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropyl acrylamide) (PNIPA) and 1 wt % nonionic or ionic (cationic and anionic) linear polyacrylamide (PAAm), were synthesized to improve the mechanical properties of PNIPA gels. The effect of the incorporation of linear polymers into responsive networks on the temperature‐induced transition, swelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with various molar ratios (25:1 to 100:1) of the monomer (N‐isopropyl acrylamide) to the crosslinker (methylenebisacrylamide). The hydrogels were characterized by the determination of the equilibrium degree of swelling at 25 °C, the compression modulus, and the effective crosslinking density, as well as the ultimate hydrogel properties, such as the tensile strength and elongation at break. The introduction of cationic and anionic linear hydrophilic PAAm into PNIPA networks increased the rate of swelling, whereas the presence of nonionic PAAm diminished it. Transition temperatures were significantly affected by both the crosslinking density and the presence of linear PAAm in the hydrogel networks. Although anionic PAAm had the greatest influence on increasing the transition temperature, the presence of nonionic PAAm caused the highest dimensional change. Semi‐interpenetrating polymer networks reinforced with cationic and nonionic PAAm exhibited higher tensile strengths and elongations at break than PNIPA hydrogels, whereas the presence of anionic PAAm caused a reduction in the mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3987–3999, 2004     

Positron annihilation lifetime study of continuous volume phase transition of poly(N-isopropylacrylamide) gel induced in methanol–water mixed solvent

The macroscopic volume shrinkage and swelling of poly(N-isopropylacryl-amide) (PNIPA) gel induced by the compositional change in the methanol–water mixed solvent is correlated to the change in the nanoscopic free volume size and numerical concentration formed in the PNIPA gels. The free volume size and numerical concentration are estimated from the longest component appearing in the positron annihilation lifetime curves. The apparent free volume fraction calculated by the free volume size and numerical concentration, and dispersion of the free volume deduced by the size distribution are utilized to analyze the origin and location of the free volumes. The free volume parameters obtained by analysis of the positron annihilation data show various nanoscopic phases occuring within the PNIPA gels during the volume change, implying the variation of the strength of the interactions among the solvent molecules and the polymer chains of the PNIPA. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1141–1151, 1998     

Lower critical solution temperature sensitivity to structural changes in poly(N‐isopropyl acrylamide) homopolymers

The effect of the molecular weight on the lower critical solution temperature (LCST) has been discussed extensively, where LCST increased with molar mass, decreased or kept constant, which leads to confusion. This work is focused on the preparation of poly(N‐isopropyl acrylamide) homopolymers, obtained in a wide molecular weights range. The LCST behavior is analyzed by calorimetry and rheology, and a deep study of molecular features is carried out for a better knowledge of the influence of various parameters involved on LCST. Finally, the molecular weight trend is observed, and its influence on LCST is compared with the effect of other parameters as polymer concentration in water, end‐group effect, and tacticity. It is observed that other parameters such tacticity and end‐group effect will affect the LCST behavior over molecular weight, if this one is not high enough. Furthermore, the study of the LCST ranges will be a useful tool for analyzing the molecular weight trends. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1386–1393     

Phase separation in poly(N‐isopropyl acrylamide)/water solutions. II. Salt effects on cloud‐point curves and gelation

The cloud‐point temperatures (T_clo's) of poly(N‐isopropyl acrylamide) (PNIPAM)/water solutions with NaCl, NaBr, or NaI were measured. All these salts reduced the T_clo's of PNIPAM/water solutions to different extents, in the following order: NaCl > NaBr > NaI. The higher the concentration of the added salt was, the more greatly T_clo dropped. A dynamic viscoelasticity investigation of the PNIPAM/water solutions with the salts indicated that during phase separation, the system changed from a homogeneous fluid into a physically crosslinked network, and the addition of salts also reduced the temperature at which this change began. The gelation temperature (T_gel) and the scaling exponent of the PNIPAM/water solutions with NaBr were obtained with dynamic scaling theory, and T_gel was found to be close to T_clo. That the addition of salts to the solution decreased T_clo and T_gel to the same extent further proved that the network structure was formed with the phase separation in the PNIPAM/water solutions. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 901–907, 2001     

Exploration of high‐resolution ultrasonic spectroscopy as an analytical tool to study demixing and remixing in poly(N‐isopropyl acrylamide)/water solutions

The ultrasonic properties of poly(N‐isopropyl acrylamide) (PNIPAM)/water solutions, determined with high‐resolution ultrasonic spectroscopy (HR‐US), change during demixing and remixing. All HR‐US measurements are discussed with respect to modulated temperature differential scanning calorimetry results. The lower critical solution temperature type of phase behavior, in combination with the glass‐transition/composition curve of PNIPAM/water, determines the evolution of the ultrasonic signals. Three different temperature regions can be distinguished: a homogeneous region and a heterogeneous region, the latter subdivided into zones without and with interference of partial vitrification of the PNIPAM‐rich phase. During phase separation, the ultrasonic velocity decreases because of a change in the hydration structure around the polymer chains, whereas the ultrasonic attenuation increases as aggregation sets in. Isothermal measurements clearly show time dependence for both the velocity and the attenuation. The observed timescales are different and can be related to a changing polymer/water interphase and aggregate formation, respectively. Partial vitrification of the PNIPAM‐rich phase slows the demixing kinetics and especially the remixing kinetics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1283–1295, 2005     

Free‐volume change in volume phase transition of polyacrylamide gel as studied by positron annihilation: Salt dependence

Variation of free‐volume parameters—average radius size, number concentration, and size distribution—of a polyacrylamide (PAAm) gel containing 4 mol % carboxylate anions is studied during a volume phase transition (VPT) caused by a change of sodium chloride (NaCl) concentration. A positron annihilation lifetime technique is used for the determination of the free‐volume characteristics. The measurement is performed in an acetone–water 3 : 2 (v/v) [0.27 : 0.73 (mol/mol)] mixed solvent at 20°C, and the free‐volume parameters deduced from the analysis of a positron annihilation curve are utilized. An average free‐volume size of the swollen PAAm gel, ∼ 0.32 nm in radius, almost agrees with that of the mixed solvent for a corresponding salt concentration, while the size of the collapsed gel, which is ∼ 0.28 nm in radius, is smaller than that of the mixed solvent. The results for the collapsed gel indicate that the hydrogen bond plays a significant role in the nanoscopic environment. The radius of the free‐volume of the swollen PAAm gel seems to be influenced by the composition between acetone and water. An inhomogeneity of the nanoscopic structure inside the PAAm gels is discussed in terms of a dispersion of a size distribution of the free‐volume. It is concluded that a change of the nanoscopic environment of the PAAm gel during the VPT can be monitored through the free‐volume parameters obtained by the positron annihilation lifetime technique. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2634–2641, 1999     

Hydration‐mediated effects of saccharide stereochemistry on poly(N‐isopropylacrylamide) gel swelling

To shed new light on the mechanisms of saccharide stereochemistry effect on macromolecules in aqueous solutions, we studied the effect of three monosaccharide stereoisomers, glucose, galactose, and mannose, on the swelling of Poly(N‐isopropylacrylamide) (PNIPA) hydrogels. We equilibrated PNIPA hydrogels in sugar solutions of different concentrations at 25 °C, and determined gel volume and mass swelling ratios, and sugar concentration imbalance. The volume‐phase‐transition occurred at molal concentrations of 0.587 ± 0.004 (galactose), 0.724 ± 0.003 (glucose), and 0.846 ± 0.004 (mannose). The same order of sugars emerged for the gel‐swelling and the magnitude of the sugar concentration‐imbalance, which correlated with sugar isentropic molar compressibility and hydration number. The more hydrated the sugar, the worse a cosolvent it is for the polymer, hence the larger the deswelling and the more negative the sugar concentration imbalance. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Free volume‐size dependence on temperature and average molecular‐weight in poly(ethylene oxide) determined by positron annihilation lifetime spectroscopy

Positron lifetime measurements were carried out in a series of poly(ethylene oxide)—PEO—of different average molecular weights (M _w): 1000, 1500, 6000, 10,000, 300,000, and 4 M. The mean radius (R ) and the mean free volume size (V_f) values were determined using a semiempirical equation that correlates the ortho‐positronium (o‐Ps) lifetime (τ₃) and size of holes existing in the amorphous phases. The hole mean radius values determined at room temperature from lifetime spectra were found to be between 2.68 and 2.97 Å, and the hole volumes between 80 and 110 ų. Free volume size evolution was studied with temperature variation until the melting temperature of the PEO samples. The degree of crystallinity and the melting temperatures were determined by Differential Scanning Calorimetry. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 219–226, 1999     

Positron annihilation and differential scanning calorimetry studies of polyacrylamide and poly(dimethylacrylamide)/poly(ethylene glycol) blends

Positron annihilation lifetime spectroscopy and differential scanning calorimetry (DSC) measurements were performed for blends of polyacrylamide (PAM) and poly(ethylene glycol) (PEG) and blends of poly(dimethylacrylamide) (PDMAM) and PEG. The samples were prepared by codissolution in a concentration range of 0–100 wt % PEG. The thermal behavior, characterized by DSC measurements, showed similar variations of the glass‐transition temperatures (T_g's) with the PEG concentration for the two systems. Pure PAM and PDMAM presented T_g's of 188 and 111 °C, respectively. A relatively small and nearly linearly decreasing T_g was observed for the two systems in the range of 20–80 wt % PEG. PEG crystals were present in all blend compositions, and no melting point depression was observed. The thermal results pointed to the partial miscibility of the blends. The degree of crystallinity of PEG increased with increasing PEG concentration for the PDMAM/PEG systems. The ortho‐positronium lifetime (τ₃) increased with increasing PEG concentration for both blends. However, the parameter of the ortho‐positronium formation probability (I₃) decreased with the PEG concentration. The product τI₃, which was proportional to the total free volume fraction, was approximately constant with the PEG concentration for PDMAM blends and increased with the PEG concentration for PAM systems. This result may be interpreted as a consequence of a more heterogeneous structure in PAM blends. Scanning electron microscopy micrographs of blends with 40 and 80 wt % PEG provided evidence of the regions associated with PEG crystallites. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1493–1500, 2003     

Characterization of poly(silylenemethylene)s by positron annihilation lifetime spectroscopy. I.

Amorphous and crystalline poly(silylenemethylene)s with the repeating PhRSiCH₂ (R : Me or Ph) units were characterized by positron annihilation lifetime spectroscopy (PALS) to gain insights into the molecular motions of these polymers. The temperature dependence of the ortho-positronium lifetime (τ₃) and intensity (I₃) was examined from 50 to 470 K for each sample. The glass transition temperature of each polymer was easily distinguished by a change in the slope of τ₃ spectrum. Both polymers exhibited a steep drop of I₃ at 130–140 K being probably assignable to the transition arising from the motions of phenyl groups, which was almost undetectable by means of differential scanning calorimetry or dynamic mechanical analysis. Several other transitions of these polymers detected by PALS are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 755–761, 1998     

Free Volume and Swelling in Thin Films of Poly(N‐isopropylacrylamide) End‐Capped with n‐Butyltrithiocarbonate

The free volume in thin films of poly(N‐isopropylacrylamid) end‐capped with n‐butyltriocarbonate (nbc‐PNIPAM) is probed with positron annihilation lifetime spectroscopy (PALS). The PALS measurements are performed as function of energy to obtain depth profiles of the free volume of nbc‐PNIPAM films. The range of nbc‐PNIPAM films with thicknesses from 40 to 200 nm is focused. With decreasing film thickness the free volume increases in good agreement with an increase in the maximum swelling capability of the nbc‐PNIPAM films. Thus in thin hydrogel films the sorption and swelling behavior is governed by free volume.

     

Constraints and thermal expansion of the free volume in a micro‐phase separated poly(ester‐adipate)urethane

The free volume behavior of a thermoplastic polyesterurethane (TPU) versus temperature is investigated by positron annihilation lifetime spectroscopy and dilatometry. A discrepancy with the free volume predicted by the lattice‐hole theory is found. The agreement is restored by assuming anisotropic expansion of the free volume holes, which in fact results in expansion mainly in two dimensions. This finding is perfectly compatible with a polymer structure based on rheological, thermal, and TEM data which envisage TPU as formed by short soft segments limited in their movements by chain connectivity and confined by physical crosslinks due to the hard segments. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2104–2109     

Swelling behavior of poly{N‐[3‐(dimethylaminopropyl)] methacrylamide‐co‐acrylamide} hydrogels in aqueous solutions of surfactants

Temperature sensitive poly{N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐acrylamide} [P(DMAPMA‐co‐AAm)] hydrogels were prepared by the free‐radical crosslinking copolymerization of corresponding monomers in water with N,N‐methylenebisacrylamide as the crosslinker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylethylenediamine as the activator. The swelling equilibrium of the P(DMAPMA‐co‐AAm) hydrogels was investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate and the cationic surfactant dodecyltrimethylammonium bromide. In pure water, regardless of the amount of N,N‐methylenebisacrylamide, the P(DMAPMA‐co‐AAm) hydrogels showed a discontinuous phase transition between 30 and 36 °C. However, the transition temperature changed from discontinuous to continuous with the addition of surfactants; this was ascribed to the conversion of nonionic P(DMAPMA‐co‐AAm) hydrogels into polyelectrolyte hydrogels due to the binding of surfactants through hydrophobic interactions. Additionally, the concentrations of free sodium dodecyl sulfate and dodecyltrimethylammonium bromide ions were measured at different temperatures by conductometry, and it was found that the electric conductivity of the P(DMAPMA‐co‐AAm)–surfactant systems depended strongly on the swelling ratio; most notably, it changed drastically near the phase‐transition temperature of the P(DMAPMA‐co‐AAm) hydrogel. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1645–1652, 2006     

Super macroporous poly(N‐isopropyl acrylamide) cryogel for separation purpose

Polymers that can respond reversibly by changing their physical or chemical properties are recognized as stimuli‐responsive polymers. The renowned temperature‐sensitive polymer is poly(N‐isopropyl acrylamide) (p(NIPAM)), and here, homopolymeric supermacroporous p(NIPAM)) cryogel was synthesized via cryopolymerization technique at cryogenic condition (below melting point of solvent, −18°C). Then, the prepared p(NIPAM) cryogel was characterized via scanning electron microscopy, Fourier transform infrared radiation spectrometer, and thermogravimetric analyzer. The lower critical solution temperature (LCST) value of the prepared p(NIPAM) cryogel was determined from % swelling equilibrium swellings at various temperatures, 20, 25, 30, 35, 40, 45, and 50°C, respectively. Furthermore, the pore volume and porosity of p(NIPAM) cryogels were compared below and above the LCST values. Finally, the separation capability of p(NIPAM) cryogels for some molecules such as tannic acid, gallic acid, nicotine (N), and caffeine (C) was investigated at the below and above the LCST values.     

Effect of physical aging of poly(1‐trimethylsilyl‐1‐propyne) films synthesized with TaCl5 and NbCl5 on gas permeability,fractional free volume,and positron annihilation lifetime spectroscopy parameters

The effect of physical aging on the gas permeability, fractional free volume (FFV), and positron annihilation lifetime spectroscopy (PALS) parameters of dense, isotropic poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) films synthesized with TaCl₅ and NbCl₅ was characterized. As‐cast films were soaked in methanol until an equilibrium amount of methanol was absorbed by the polymer. When the films were removed from methanol, film thickness initially decreased rapidly and was almost constant after 70 h in air for both catalysts. This timescale was much longer than the timescale for complete methanol desorption (ca. 5 h). From the film‐thickness data, the reduction in FFV with time was estimated. For samples prepared with either catalyst, the kinetics of FFV reduction were well‐described by a simple model based on the notion either that free‐volume elements diffuse to the surface of the polymer film and are subsequently eliminated from the sample or that lattice contraction controls polymer densification. Methane permeability decreased rapidly during the first 70 h, which was the same timescale for the thickness change. The decrease in methane permeability was smaller in films prepared with NbCl₅ than with TaCl₅. The logarithm of methane permeability decreased linearly as reciprocal FFV increased, in accordance with free‐volume theory. The PALS results indicate that the concentration of larger free‐volume elements (as indicated by the intensity I₄) decreased with aging time and that the other PALS parameters were not strongly influenced by aging. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1222–1239, 2000     

Atypical transition temperature dependence of poly(N‐isopropylacrylamide) and poly(N‐isopropylacrylamide‐co‐acrylamide) nanocomposites on the content of exfoliated montmorillonites

Exfoliated montmorillonite (MMT)/poly(N‐isopropylacrylamide) (PNIPAAm) and MMT/poly(N‐isopropylacrylamide‐co‐acrylamide) [P(NIPAAm‐co‐AAm)] nanocomposites were fabricated by soap‐free emulsion polymerization. Interestingly, as the content of MMT was increased from 0 to 10 wt %, the glass transition temperature of MMT/PNIPAAm was decreased from 145 to 122 °C, whereas that of the MMT/P(NIPAAm‐co‐AAm) increased from 95 to 153 °C. Although the lower critical solution temperature (LCST) of 32 °C for the MMT/PNIPAAm nanocomposites in aqueous solutions was slightly increased with the content of MMT, that of the MMT/P(NIPAAm‐co‐AAm) was decreased from 70 to 65 °C. A mechanism that the hydrogen bonds between the amide groups of PNIPAAm were interfered by the exfoliated MMT nano‐platelets for the MMT/PNIPAAm nanocomposites and the preferred absorption of acrylamide units to the MMT nanoplatelets rather than N‐isopropylacrylamide in the MMT/P(NIPAAm‐co‐AAm) nanocomposites was suggested to interpret these unusual transition behavior. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 524–530, 2009     

Novel poly(N‐isopropylacrylamide)/clay/poly(acrylamide) IPN hydrogels with the response rate and drug release controlled by clay content

Novel interpenetrating network (IPN) hydrogels (PNIPAAm/clay/PAAm hydrogels) based on poly(N‐isopropylacrylamide) (PNIPAAm) crosslinked by inorganic clay and poly(acrylamide) (PAAm) crosslinked by organic crosslinker were prepared in situ by ultraviolet (UV) irradiation polymerization. The effects of clay content on temperature dependence of equilibrium swelling ratio, deswelling behavior, thermal behavior, and the interior morphology of resultant IPN hydrogels were investigated with the help of Fourier transform infrared spectroscopy, differential scanning calorimeter (DSC), scanning electron microscope (SEM). Study on temperature dependence of equilibrium swelling ratio showed that all IPN hydrogels exhibited temperature‐sensitivity. DSC further revealed that the temperature‐sensitivity was weakened with increasing amount of clay. Study on deswelling behavior revealed that IPN hydrogels had much faster response rate when comparing with PNIPAAm/clay hydrogels, and the response rate of IPN hydrogels could be controlled by clay content. SEM revealed that there existed difference in the interior morphology of IPN hydrogels between 20 [below lower critical solution temperature (LCST)] and 50 °C (above LCST), and this difference would become obvious with a decrease in clay content. For the standpoint of applications, oscillating swelling/deswelling behavior was investigated to determine whether properties of IPN hydrogels would be stable for potential applications. Bovine serum albumin (BSA) was used as model drug for in vitro experiment, the release data suggested that the controlled drug release could be achieved by modulating clay content. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 96–106, 2009