A comparison of the swelling behaviour of copolymer and interpenetrating network microgel particles

 A comparison of the swelling behaviour of two types of hydrogel particles, namely, random poly[(acrylic acid)-co-(acrylamide)] [P(AAc-co-AAm)] particles and PAAc/PAAm interpenetrating network (IPN) particles, has been made using temperature and pH as the triggers. Both types of particles were synthesised by inverse microemulsion polymerisation. The conversion yield of AAc was found to be around 60 wt% due to the partition of this monomer between the aqueous and organic phases. The AAc content was thus lower in the final particles than in the initial composition. Both types of hydrogel particle exhibit an upper critical solution temperature associated with the breakage of the polymer–polymer hydrogen bonds. The maximum swelling ratio occurred in both cases at approximately equimolar AAc and AAm content of the particles. A sharper swelling transition was observed for the PAAc/PAAm IPN particles. This is because of the co-operative nature of the interactions between the PAAc and PAAm chains, the so-called “zipper effect”. A very much higher swelling ratio was obtained using pH as the trigger compared to using temperature. This difference in behaviour is related to the relative strengths of the forces involved in the particle swelling. Electrostatic repulsion forces, associated with the AAc dissociation with increasing pH, are much stronger than the hydrogen bonds. Received: 18 August 1999/Accepted: 28 August 1999     

Swelling behavior of poly- N-isopropylacrylamide microgel particles in alcoholic solutions

 It has been shown that the swelling of poly-N-isopropyl-acrylamide (poly-NIPAM) microgel particles can be controlled by the addition of alcohols, in addition to the previously observed effect of temperature. The degree of swelling is also controlled by the amount of cross-linker within the microgel particles. At 25 ^°C, poly-NIPAM microgel particles collapse upon the addition of MeOH, EtOH and 2-PrOH to a minimum size and then, reswell again as the alcohol-rich region is approached. This trend was also observed for poly-NIPAM microgel particles dispersed in 2-PrOH/water mixtures upon heating to 50 ^°C. The particles, dispersed in either water or alcohol/water mixtures were found to be stable to flocculation between 25 ^°C and 50 ^°C. Received: 27 February 1997 Accepted: 5 August 1997     

The electrophoresis of poly(N-isopropylacrylamide) microgel particles

 The electrophoretic mobility of a poly(N-isopropylacrylamide) microgel containing carboxylic groups has been measured as a function of the ionic strength, between 0.1 and 100 mM NaCl, over the temperature range 2545 ^∘C. The mobility data obtained have been evaluated using different models, including the porous-sphere, the soft-plate and the soft-sphere models as well as the hard-sphere model developed by Henry and later refined by O'Brien and White. The “porous” or “soft” behaviour is evident at lower temperatures, whereas at higher temperatures none of the models can fully explain the observed behaviour. It is suggested that the discrepancies at higher temperatures can be partly ascribed to the neglect of the relaxation effect in the “soft” models. Received: 30 June 1999/Accepted in revised form: 12 October 1999     

Stress-induced compaction of concentrated dispersions of gel particles

 When submitted to successive shear stress steps, the elastic shear modulus of a concentrated dispersion of soft gel particles shows an exponential increase from 50 to 110 Pa. A slow relaxation time (τ _r ≃500 s) attributed to the mobility of the gel particles within their free volume is obtained. The amplitude of the relaxation time distribution decreases with the number of shear stress sequences, indicating a progressive decrease in the free volume available per particle. The results are explained by an increase in the packing density as grains rearrange under the external constraint. A rate constant is determined from the evolution of the dispersion's elastic modulus (K≃4 × 10⁻⁴ s⁻¹). The rate of compaction shows a logarithmic decrease when the initial particle's packing fraction is increased. Received: 5 October 1999 In revised form: 21 December 1999 Accepted: 21 January 2000     

Anomalous electrophoretic mobility of microgel particles in buffer solutions

The electrophoretic mobility (μ) of tunable surface charge poly(N-isopropylacrylamide) microgel particles (PNIPAM) was measured vs pH, using different anionic buffers. Two minima, just at the buffers’ pK values, were found for the μ-pH curve. The preferential penetration of the small counterions into the soft-charged shell explains the electrokinetic charge reduction. For pH values higher than the pK, the charge screening leads to electrostatic repulsions among coions. It pushes them towards the particles; thus, balancing the global ionic distribution.     

Structure and polymer dynamics within PNIPAM-based microgel particles

The synthesis of temperature-responsive microgels of poly(N-isopropylacrylamide) (PNIPAM) was first reported in 1986 and, since then, there have been hundreds of publications describing the preparation, characterization and applications of these systems. This paper reviews the developments concerning the study of the structure of PNIPAM-based microgels performed over the last years using small angle neutron scattering (SANS) and also the investigations of the polymer-chain dynamics within the microgels carried out with incoherent elastic and quasielastic neutron scattering, and pulse field gradient nuclear magnetic resonance (PFG-NMR) techniques. Furthermore, the self-diffusion coefficient of the water molecules within the microgel, determined by means of solvent relaxation NMR, is also discussed as a function of the polymer volume fraction of the microgels.     

Characterization of cross-linked poly(N-isopropylmethacrylamide) microgel latexes

 This article reports the colloidal and physicochemical characterization of crosslinked poly (N-isopropylmethacrylamide) (poly[NIPMAM]) latexes. The latex particles were first characterized by determining the lowest critical solubility temperature by measuring the optical density variation as a function of temperature. In addition, the electrophoretic mobility behaviors of all latexes were examined as a function of pH and temperature. Finally, the colloidal stability was investigated by determining the critical coagulation concentration and the critical flocculation temperature, and the corresponding results were discussed by taking into account both the effect of salinity and temperature on the solvency of poly[NIPMAM]. Received: 25 March 1999 Accepted: 5 May 1999     

Production of hollow polymer particles by suspension polymerization

 Polymer particles having single hollow in the inside were successfully prepared by suspension polymerization for divinylbenzene/ toluene droplets dissolving polystyrene (PS) in an aqueous solution of poly(vinyl alcohol). Such a hollow polymer particle was not obtained without PS. The hollow structure was affected by the molecular weight and the concentration of PS. Received: 3 December 1997 Accepted: 27 March 1998     

Colloidal crystals made of poly(N-isopropylacrylamide) microgel particles

Poly (N-isopropylacrylamide) microgel particles are found to form colloidal crystals similar to those occurring in typical hard-sphere colloids like poly(methylmethacrylate) beads. Samples made of particles with different cross-linker concentrations are investigated and their deswelling ratio is determined using dynamic light scattering. Small-angle neutron scattering data are also presented and analysed in terms of a face-centred-cubic crystal structure. The characteristic length, a, of the elementary cell is found to be 535 ± 16 and 495 ± 15 nm for the two systems investigated. This leads to particle radii of 189 ± 6 and 175 ± 5 nm, respectively. These values compare well to the radii determined using several different methods. Received: 26 July 1999/Accepted: 21 March 2000     

Study of the dissolution process of polystyrene in concentrated cyclohexane solution by MNR relaxation

 ¹³C-NMR relaxation times of polystyrene (PS) chains in its theta solvent, cyclohexane, have been measured at different temperatures. It was found that relaxation of carbon nuclei of the side-chain-phenyl groups and those of main chains have remarkably different temperature-dependent relaxation behaviors in the solvent. A two-step model for the dissolution process is proposed. According to the model, swelling of the polymer below θ temperature corresponds mainly to the gradual dispersion of the side-chain phenyl groups; while the complete dissolution above θ temperature corresponds mainly to the gradual dispersion of the main chains at a molecular level. These dispersions reflect the fact that cohesional interaction among side-chain-phenyl rings or main chains are weakened by solvent molecules, which shows the existence of the cohesional entanglements among polymer chains. The results of T ₁(C) are confirmed by the biexponential dependence of ¹H-NMR spin–spin relaxation on temperature. Received: 2 July 1997 Accepted: 21 October 1997     

Production of multi-hollow polymer particles by the stepwise acid/alkali method

 Recently, we reported that multi-hollow polymer particles can be prepared from carboxylated polymer particles by the stepwise alkali/acid method. In this article, an attempt was made to prepare similar particles from acid-swellable polymer particles by the stepwise treatment with acid and alkali, which was named the stepwise acid/alkali method. The acid-swellable particles were produced by emulsion terpolymerization of styrene, butyl acrylate, and dimethyl 2-amino ethyl methacrylate. The effects of initial pH value, temperature, and time in the acid and alkali treatment processes on the multi-hollow structure were examined. Received: 18 December 1996 Accepted: 11 March 1997     

Dielectric analysis of polystyrene microcapsules using scanning dielectric microscope

 A dielectric imaging technique with a scanning dielectric microscope was applied to polystyrene microcapsules in an aqueous environment to study the electrical properties of individual ones. The dielectric images obtained over a frequency range from 10 kHz to 10 MHz showed frequency dependence, which indicated dielectric dispersion (or relaxation) due to interfacial polarization or the build up of charge on the boundaries between the microcapsule shell and the aqueous phases. The dielectric dispersion was analyzed based on an equivalent electrical circuit model and a shell-sphere model in which a spherical core is covered with an insulating shell. Received: 26 September 1997 Accepted: 26 December 1997     

Morphology of micron-sized monodispersed composite polymer particles produced by seeded polymerization for the dispersion of highly monomer-swollen polymer particles

 Monodispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles having 9.4 μm in diameter were produced by seeded polymerization for the dispersion of highly n-butyl methacrylate (BMA)-swollen PS particles, and their morphologies were examined. The highly BMA-swollen PS particles (about 150 times the weight of the PS seed particles) were prepared by mixing monodispersed 1.8 μm-sized PS seed particles and 0.7 μm sized BMA droplets prepared with an ultrasonic homogenizer in ethanol/water (1/2, w/w) medium at room temperature. After NaNO₂ aqueous solution as inhibitor was added in the dispersion, the seeded polymerization was carried out at 70 °C. In an optical microscopic observation, one or two spherical high contrast regions which consisted mainly of PS were observed inside PS/PBMA composite particles. In the PS domain, there were many fine spherical PBMA domains. Such morphologies were based on the phase separation of PS and PBMA within the homogeneous swollen particles during the seeded polymerization. Received: 04 June 1997 Accepted: 27 August 1997     

Influence of adsorbed polymers on the removal of mineral particles from a planar surface

 Experimental results on the role of adsorbed polymers on the particle adhesion are presented. Both Brownian (silica particles) and non-Brownian (glass beads) particles were used. The particles were deposited onto the internal surface of a glass parallelepiped cell, and then submitted to increasing laminar flow rates. The pH and the ionic strength of the electrolytes were fixed. The adhesive force was related to the hydrodynamic force required to dislodge 50% of the initially attached beads. We found that high molecular weight PEO had little effect on the adhesion of small silica beads due to the low affinity of the polymer for silica or glass surfaces. On the contrary, PEO greatly enhanced the adhesion of bigger glass beads forced to deposit on the capillary surface because of gravity. The increase was all the more pronounced as the molecular weight of the polymer was high. The effect of high molecular weight cationic copolymers on the adhesion of silica particles was drastic. The maximal force (1500 pN) applied by the device could not enable any particle detachment even using polymers of low cationicity rate (5%), showing the efficiency of electrostatic attractions. When copolymers were adsorbed on both surfaces (particles and plane), the adhesive force exhibited a maximum at intermediate coverage of particles. This optimum was related to the optimum flocculation concentration classically observed in flocculation of suspensions by polymers. Received: 16 February 1996 Accepted: 10 September 1996     

Thermal response of a microgel system

Recent experimental studies [Z. Wu, B. Zhou, Z.B. Hu, Phys. Rev. Lett. 90 (2003) 048304] on an uncharged aqueous poly-N-isopropylacrylamide (PNIPAM) dispersion have shown that this microgel system is sensitive to temperature. This system was also experimentally found to be modeled quite well by microgel particles interacting via a hard-sphere repulsive plus an inverse power (temperature-dependent) attractive potential. To understand theoretically this thermally responsive PNIPAM dispersion, we apply a novel approach [G.F. Wang, S.K. Lai, Phys. Rev. E 70 (2004) 051402] to calculate its thermodynamic phase diagram. Differing from the conventional method in which the boundaries of the coexisting phases are the ultimate target, the present work places emphasis on crosshatching colloidal domains which include the homogeneous phase (gas, liquid or solid), two coexisting phases and perhaps also multi-phases in coexistence. Strategically, this was done by treating the coexisting phases as one composite system whose Helmholtz free energy density is written as the sum of constituent free energy densities each of which is weighed by its respective volume proportion. We show here that by minimizing the composite system's free energy density the phase-diagram domains can all be determined in addition to the phase boundaries customarily obtained by imposing the conditions of equal pressure and equal chemical potential. Also, we present the theoretically predicted phase diagram of PNIPAM dispersion and compare it with the one observed experimentally.     

Uptake and release of surfactants from polyampholyte microgel particles

Polyampholyte microgel particles, containing both methacrylic acid and 2-(dimethylamino) ethyl methacrylate (a weak base), in a mainly N-isopropyl acrylamide network, have been prepared by free-radical dispersion polymerisation. The swelling properties of the particles have been shown to be pH and temperature dependent and to exhibit a minimum in size at the iso-electric point. The uptake and release of cetylpyridinium chloride and Triton X-100, into and from, the polyampholyte microgel particles have been investigated as a function of pH. The absorbed amounts at different pH values have been related to various specific interactions between the surfactant and the microgel network.     

Preparation of thermosensitive nanogels by photo-cross-linking

 A novel method to prepare thermosensitive nanogels from photocross-linkable copolymers of N-isopropylacrylamide and dimethyl maleinimido acrylamide (DMIAAm) was developed. The colloidal nanogels were formed by UV irradiation of solutions of thermosensitive polymers in water at 45 °C. The compositions of the photopolymer solutions were varied by changing the amount of DMIAAm in the photopolymer chains (2–10 mol%) or by varying the sodium dodecyl sulfate (SDS) concentration. The resultant nanogel particles were rather spherical and showed large changes in hydrodynamic diameters in the vicinity of the phase transition temperature of the corresponding linear photopolymers. The particle sizes of the nanogels and their swellability could be controlled through the UV irradiation time, the chromophore content and the SDS concentration. An increase in the chromophore content and the SDS concentration resulted in nanogels with smaller dimensions. The hydrodynamic diameters of the nanogels decreased significantly from 2 to 10 min UV irradiation time but not significantly after that. The phase transition of the photopolymer solutions and the respective nanogels could be adjusted by the chromophore content or the SDS concentration. An increase in the chromophore content leads to lower phase-transition temperatures, whilst an increase in the SDS concentration elevated them. Pulsed-field-gradient NMR proved a useful tool to investigate the network formation in the nanogels by determining changes in the diffusion coefficients. Received: 14 May 2001 Accepted: 1 June 2001     

Morphology of anomalous polystyrene/ polybutyl acrylate composite particles produced by seeded emulsion polymerization

 Recently, we found that “golf ball”-like polystyrene (PS)/polybutyl acrylate (PBA) composite particles could be produced by seeded emulsion polymerization of butyl acrylate (BA) with PS seed particles. In this article, the effects of the polymerization temperature, BA monomer concentration, and the presence of 1-octanol, which is a good solvent for PBA and a poor solvent for PS in the polymerization, on the morphology was studied. Received: 25 February 1997 Accepted: 4 October 1997     

Micron-sized monodispersed polymer particles produced by seeded polymerization for the dispersion of high swelling of polymer particles with a large amount of monomer

 Micron-sized monodispersed polystyrene (PS)/poly(n-butyl methacrylate) composite particles were produced as follows. First, 1.77 μm-sized monodispersed PS seed particles produced by dispersion polymerization were dispersed in ethanol/water (1/2, w/w) medium dissolving poly(vinyl alcohol) as a stabilizer. n-Butyl methacrylate (BMA) monomer dissolving benzoyl peroxide initiator was emulsified in ethanol/water (1/2, w/w) solution of sodium dodecyl sulfate as emulsifier with ultrasonic homogenizer, and the BMA monomer emulsion was mixed with the PS seed emulsion. The PS seed particles absorbed with a large amount of BMA (about 150 times weight of the seed particles) for 2 h to about 10 μm in diameter while keeping good monodispersity and BMA droplets disappeared finally. The seeded polymerization was carried out at 70 °C after a certain amount of water was added to depress the redissolving of BMA from the swollen particles into the medium by raising from room temperature to the polymerzation temperature. Received: 21 February 1996 Accepted: 4 September 1996     

Influence of the swelling state of seed polymer particles with monomer on the morphology of micron-sized monodispersed composite polymer particles produced by seeded polymerization utilizing the dynamic swelling method

 Micron-sized mono-dispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles (PS/PBMA=2/1 by weight) having a heterogeneous structure in which many fine PBMA domains dispersed in a PS matrix near the particle surface were produced by seeded polymerization of n-butyl methacrylate (BMA) of which almost all had been absorbed by 1.8 μm-sized monodispersed PS seed particles utilizing the dynamic swelling method. The morphology was varied by changing the PS/BMA ratio and polymerization temperature. It was concluded that the swelling state of 2 μm-sized BMA-swollen PS particles in the seeded polymerization process is one of the important factors to control the morphology of the composite particles. Received: 27 November 1996 Accepted: 21 March 1997