Microstructure and rheology of stimuli-responsive nanocolloidal systems-effect of ionic strength

The effect of ionic strength on the rheological behavior of model pH-responsive nanocolloidal systems consisting of methacrylic acid-ethyl acrylate (MAA-EA) cross-linked with diallyl phthalate (DAP) was examined. Neutralization of acid groups increases the osmotic pressure exerted by counterions trapped in the polymeric network against ions in bulk solution, which is responsible for the swelling and increase in viscosity. Swelling decreases with increasing salt concentration as a result of reduced osmotic pressure inside the microgels, which is attributed to the charge shielding effect of counterions (salt) on the negatively charged carboxylate groups. Electromotive measurements using ion-selective electrodes confirmed that not all the counterions, that is, K+, remain mobile, but a fraction of these ions can penetrate the porous microgel particles to shield the negatively charged carboxylate groups. A consequence of this is that some of the Na+ counterions inside the particles are expelled, thus regaining their translational entropy, and become mobile sodium ions in the bulk solution. We successfully developed a new scaling law that relates the swelling ratio, Q, of microgels as a function of neutralization degree, alpha, cross-linked density, Nx, molar fraction of acidic units, y, and concentration of mobile counterions, CK+ and CNa+, represented as (Nx/c0)(CK+ + CNa+Q + Q2/3 proportional, variant yNxalpha. The new scaling law no longer assumes that all the counterions are trapped inside the microgels. The proportionality reduces to the form Q proportional, variant (yalphaNx)3/2 in the absence of salt, that is, CK+ + CNa+ approximately 0. By combining the results from light scattering and rheological measurements, we are able to correlate the microstructural evolution of the colloidal systems with their bulk rheological behavior.     

Review on the dynamics and micro-structure of pH-responsive nano-colloidal systems

This review presents an overview on the research on pH-responsive microgel particles in the last 10 years. Microgels are cross-linked latex particles that are swollen in a good solvent. Significant quantitative studies have been conducted to investigate the swelling behavior (microscopic) and rheological (macroscopic) properties of the pH-responsive microgel particles as a function of neutralization degree, ionic strength, and cross-linked density. Mono-dispersed, alkali-swellable microgels containing carboxylic acid lattices, whose properties display extreme pH sensitivity in water is considered in detail in terms of swelling behavior and rheological properties. Their stability in solution and ability to undergo reversible volume phase transitions in response to pH makes them ideal model systems for the development of a semi-empirical as well as theoretical approach for predicting the viscosity of dilute and concentrated hard and soft sphere systems. The review concludes with a discussion of some recent applications of pH-responsive microgel particles.     

Inducing pH responsiveness via ultralow thiol content in polyacrylamide (micro)gels with labile crosslinks

Here we present the synthesis and characterization of pH responsive polyacrylamide microgels, synthesized via free radical polymerization of acrylamide and bis (acryloylcystamine) (BAC). The gels were made with ultralow amounts of thiol functional groups incorporated into the polymer. The resulting gel monoliths were mechanically chopped into microgel particles with size distributions ranging from 80 to 200 mum. The gels exhibit an interesting reversible pH-dependent rheological behavior which led to gelling of the colloidal suspension when the pH was increased, and a low-viscosity suspension was obtained when the pH was taken back to the original value. The viscosity of the colloidal system containing MBA crosslinked microgels remained insensitive to pH. This observation motivated further analysis; viscosity measurements of the highly viscous (gel-like) state of the BAC crosslinked microgel colloidal suspension were carried out to further understand the rheological behavior of the colloidal system. Electrophoretic mobility measurements as function of pH of the BAC and MBA crosslinked colloidal polyacrylamide microgel suspensions were performed. The swelling behavior of the microgels for both colloidal systems was also determined as function of pH using static light scattering. This swelling behavior was used to rationalize the observed rheological behavior. The work presented here demonstrates that free thiol groups present within a polymer gel matrix confer pH responsive behavior to the gel in solution. The viscosity of a BAC crosslinked microgel suspension was also measured under reducing conditions. The viscosity of the microgel suspension reduced with time, due to the breakage of the disulfide bonds in the crosslinkers.     

Structural ordering and phase behavior of charged microgels

Recent theoretical phase diagrams for loosely cross-linked ionic microgels with a low monomer volume fraction (Gottwald; et al. Phys. Rev. Lett. 2004, 92 , 068301 ) have predicted a re-entrant order-disorder transition (i.e., fluid-FCC-BCC-fluid) as a function of concentration and so far there has been no experimental verifications of these theoretical predictions. Here, we present experimental results on phase behavior of loosely cross-linked charged poly(N-isopropylacrylamide co acrylic acid) (PNIPAm-co-AAc) microgesls with a low monomer volume fraction (approximately 0.003) for a wide range of concentrations (0.02-0.6 wt %) using static and dynamic light scattering methods. These microgel dispersions exhibit a short-range liquid order at low concentration (<0.03 wt %), a FCC crystalline order at intermediate concentrations (0.03- 0.3 wt %). In addition, we suggested a possible coexistence of BCC and FCC phases at higher concentration crystalline suspension (approximately 0.34 wt %). These results clearly demonstrate the experimental verification of above theoretical prediction below the overlap concentration and also reveal that the interaction potential between the microgel particles is of screened Coulomb repulsive type within these concentration ranges. At further higher concentration (approximately 0.57 wt %), we once again observed a disordered state and this disordered state from dynamic light scattering was confirmed to be a glass. These initial results are discussed in the light of previously reported results on the phase behavior of ionic microgel colloidal dispersions.     

Influence of cross-link density on rheological properties of temperature-sensitive microgel suspensions

The influence of the cross-link density on rheological properties of thermosensitive microgels was investigated. The temperature-sensitive hydrogel particles consisted of poly (N-isopropylacrylamide) (PNiPAM) chemically cross-linked with several different molar ratios of N,N′-methylenebisacrylamide. The variation of cross-link density leads to soft spheres that possess a different particle interaction potential and a different swelling ratio. With increasing temperature the microgel particles decrease in size and with it the effective volume fraction, which leads to strong changes in rheological properties. The relative zero-shear viscosity and the plateau modulus at different temperatures superpose to mastercurves when plotted versus the effective volume fraction. Up to an effective volume fraction of 0.5 the microgels behaved like hard spheres and the maximum volume fraction, as determined from the divergence of the zero-shear viscosity, was mainly dominated by the polydispersity of the spheres and not by the cross-link density. The plateau modulus, on the other hand, revealed soft-sphere behavior and the interaction potential became softer with decreasing cross-linker content. Received: 15 December 1999 Accepted: 15 February 2000     

Interaction of nonionic surfactants with copolymer microgel particles of NIPAM and acrylic acid

Binding of the nonionic surfactants Triton X-100 and Triton X-405 onto linear copolymers of N-isopropylacrylamide (NIPAM) and acrylic acid and to cross-linked microgel particles of similar composition but differing in their cross-link densities has been studied. The binding capacities vary for each of these polymeric systems, being smallest for the linear copolymer. The binding is also significantly less in all cases for the more hydrophilic surfactant, namely, Triton X-405. By comparing estimates of the pore or "cage" size within the microgel particles with the dimensions of the free micelles in solution, it is concluded that micelles of Triton X-100 form within the microgel particles more readily for the lower cross-linked microgel particles. However, micelles do not form as easily inside either microgel for Triton X-405. The swelling/deswelling behavior of each of the two microgels, in the presence of the surfactants, has been explained in terms of their relative binding behavior and how this contributes to the osmotic pressure difference inside and outside the microgel particles and also in terms of micelle "bridging" of the polymer network, causing shrinkage.     

Osmotic compressibility of soft colloidal systems

A turbidimetric analysis of particle interaction of model pH-responsive microgel systems consisting of methacrylic acid-ethyl acrylate cross-linked with diallyl phthalate in colloidal suspensions is described. The structure factor at zero scattering angle, S(0), can be determined with good precision for wavelengths greater than 500 nm, and it measures the dispersion's resistance to particle compression. The structure factor of microgels at various cross-linked densities and ionic strengths falls onto a master curve when plotted against the effective volume fraction, phi(eff) = kc, which clearly suggests that particle interaction potential and osmotic compressibility is a function of effective volume fraction. In addition, the deviation of the structure factor, S(0), of our microgel systems with the structure factor of hard spheres, S(PY)(0), exhibits a maximum at phi(eff) approximately 0.2. Beyond this point the osmotic de-swelling force exceeds the osmotic pressure inside the soft particles resulting in particle shrinkage. Good agreement was obtained when the structural properties of our microgel systems obtained from turbidimetric analysis and rheology measurements were compared. Therefore, a simple turbidimetric analysis of these model pH-responsive microgel systems permits a quantitative evaluation of factors governing particle osmotic compressibility.     

Polymer dynamics in responsive microgels: influence of cononsolvency and microgel architecture

The dynamics of polymers on the nm and ns scales inside responsive microgels was probed by means of Neutron Spin Echo (NSE) experiments. Four different microgels were studied: poly(N-isopropylacrylamide) (PNIPAM) and poly(N,N-diethylacrylamide) (PDEAAM) microgels, a P(NIPAM-co-DEAAM) copolymer microgel and a core-shell microgel with a PDEAAM core and a PNIPAM shell. These four different microgel systems were investigated in a D(2)O/CD(3)OD solvent mixture with a molar CD(3)OD fraction of x(MeOD) = 0.2 at 10 °C. The PNIPAM and the P(NIPAM-co-DEAAM) microgels are in the collapsed state under these conditions. They behave as solid diffusing objects with only very small additional contributions from internal motions. The PDEAAM particle is swollen under these conditions and mainly Zimm segmental dynamics can be detected in the intermediate scattering function at high momentum transfer. A cross-over to a collective diffusive motion is found for smaller q-values. The shell of the PDEAAM-core-PNIPAM-shell particle is collapsed, which leads to a static contribution to S(q,t); the core, however, is swollen and Zimm segmental dynamics are observed. However, the contributions of the Zimm segmental dynamics to the scattering function are smaller as compared to the pure PDEAAM particle. Interestingly the values of the apparent solvent viscosities inside the microgels as obtained from the NSE experiments are higher than for the bulk solvent. In addition different values were obtained for the PDEAAM microgel, and the PDEAAM-core of the PDEAAM-core-PNIPAM-shell particle, respectively. We attribute the strongly increased viscosity in the PDEAAM particle to enhanced inhomogeneities, which are induced by the swelling of the particle. The different viscosity inside the PDEAAM-core of the PDEAAM-core-PNIPAM-shell microgel could be due to a confinement effect: the collapsed PNIPAM-shell restricts the swelling of the PDEAAM-core and may modify the hydrodynamic interactions in this restricted environment inside the microgel.     

Photoresponsive surfactants in microgel dispersions

Microgel particles are cross-linked polymer particles. When dispersed in a good solvent for the polymer concerned, they are able to respond to a range of external stimuli by changing volume. Hence, microgel particles are suited to numerous applications (for example, controlled uptake and release) in the pharmaceutical, coatings, and water treatment industries. In this work, pH-sensitive, 0.5 wt % cross-linked poly(2-vinylpyridine) (PVP) microgel particles have been prepared and characterized. When the dispersion pH is decreased below 4.5, the pyridine groups become protonated and the microgel network becomes positively charged, causing the particles to expand. To investigate the possibility of using light as a trigger for effecting volume changes, the interaction of these microgel particles with a photodegradable anionic surfactant, 4-hexylphenylazosulfonate (C(6)PAS), has been investigated using dynamic light scattering and electrophoretic mobility measurements. The electrostatic attraction between the positively charged microgel network (at solution pH 3) and the negatively charged headgroups on the surfactant molecules caused a dramatic decrease in particle volume, and charge-reversal of the particles occurred with increasing surfactant concentration. The UV irradiation of phenylazosulfonate surfactants destroys the anionic headgroup of the molecules, and the microgel particles re-swell. The irradiation of PVP dispersions in the presence of C(6)PAS, along with mixed surfactant systems of sodium dodecyl sulfate plus C(6)PAS, has been investigated.     

Plum-pudding gels as a platform for drug delivery: understanding the effects of the different components on the diffusion behavior of solutes

The internal structure of composite gels made of responsive microgel particles inserted into a bulk hydrogel (N-isopropylacrylamide microgel particles in a cross-linked dimethylacrylamide matrix) has been investigated from the diffusion behavior of poly(ethylene glycol) (PEG) probes through the network, in the absence of specific interactions between the diffusing molecules and the system. The effect of the different components has been examined, for example, the size of the probe, the bulk structure, and the microgel nature. Particles were characterized prior to their insertion into the hydrogel in order to describe their properties as a function of size and cross-linker content, thus revealing different swelling behaviors. The biggest effects on the diffusion of the PEG probes were related to the bulk structure, and no major effects were registered by the addition of different microgels into the hydrogel network. We attempt to rationalize this behavior in terms of the composite gel structure and discuss the results in terms of their meaning for controlled drug delivery strategies.     

Preparation of monodisperse poly(N-isopropylacrylamide) microgel particles with homogenous cross-link density distribution

Monodisperse microgel latex with homogeneous cross-link density distribution within the particles was prepared by feeding the monomer and cross-linker into the reaction mixture in a regulated way during the polymerization. To determine the appropriate monomer feeding parameters, the kinetics of the particle formation was investigated by HPLC. The swelling and optical characteristics of the prepared homogenously cross-linked microgel particles were compared to the properties of inhomogenously cross-linked microgels prepared by the normal precipitation polymerization method. The distribution of the cross-link density within the particles inserts a great influence on the characteristics of the system. The degree of swelling of the homogeneous particles is significantly higher than that of the heterogeneous microgel particles. Furthermore, at room temperature the pNIPAm latex containing the homogeneously cross-linked particles is transparent, while the heterogeneously cross-linked particles form a highly turbid system at the same 0.1 wt% concentration.     

Stimulus-responsive particulate emulsifiers based on lightly cross-linked poly(4-vinylpyridine)-silica nanocomposite microgels

Lightly cross-linked poly(4-vinylpyridine)-silica nanocomposite microgel particles have been recently reported to act as pH-responsive particulate emulsifiers [Fujii, S.; Read, E. S.; Armes, S. P.; Binks, B. P. Adv. Mater. 2005, 17, 1014]. In this work, the synthesis and performance of such nanocomposite microgel particles are studied in more detail. Scanning electron microscopy, dynamic light scattering, nitrogen microanalyses, thermogravimetric analysis, aqueous electrophoresis, and acid-base titration were used to characterize the nanocomposites in terms of their particle size and morphology, polymer and silica contents, surface compositions, and critical swelling pH, respectively. Depending on the polarity of the oil phase and the purity of the nanocomposite particles, either oil-in-water or water-in-oil emulsions could be prepared at pH 8-9, but not at pH 2-3. These emulsions were characterized in terms of their emulsion type, mean droplet diameter, and morphology using electrical conductivity, light diffraction, and both electron and optical microscopy. In some cases, rapid demulsification could be induced by lowering the solution pH: addition of acid led to protonation of the 4-vinylpyridine residues, which imparted cationic microgel character to the nanocomposite particles. Cross-linking of the nanocomposite microgel particles is essential for their optimum performance as a pH-responsive emulsifier, but unfortunately it is not sufficient to allow recycling.     

Rheology and dynamics of micellar cubic phases and related emulsions

The rheological behavior of micellar cubic phases in C12EO25 systems and related emulsions has been investigated. In the aqueous C12EO25 binary system, the transition from the cubic phase to the micellar solution is associated with a sudden drop in viscosity and with a small enthalpy of transition. The elastic modulus and viscosity of the cubic phases show a maximum with concentration but remain very high within the range of existence of the cubic phase. Several relaxation processes seem to be present in binary cubic phases, and some of them occur in a time scale that can be followed by both rheology and dynamic light scattering measurements. Upon addition of a small amount of oil (decane), the rheological behavior changes remarkably. As the oil fraction increases, the relaxation times also increase and, finally, highly concentrated, gel-like emulsions are obtained. Contrary to conventional concentrated emulsions, the viscosity of cubic-phase-based emulsions is decreased by increasing the fraction of the dispersed phase. The non-Maxwellian rheological behavior at low oil fractions is described according to the model of slipping crystalline planes, modified by using a distribution of bulk relaxation times, and good fitting to the experimental data is obtained.     

On the structure of poly(N-isopropylacrylamide) microgel particles

This investigation presents a study of the internal structure of poly(NIPAM/xBA) microgel particles (NIPAM and BA are N-isopropylacrylamide and N,N'-methylene bisacrylamide, respectively). In this study, x is the wt % of BA used during microgel synthesis. Two values of x were used to prepare the microgels, 1 and 10. The microgel dispersions were investigated using photon correlation spectroscopy (PCS) and small-angle neutron scattering (SANS). These measurements were made as a function of temperature in the range 30-50 degrees C. Scattering maxima were observed for the microgels when the dispersion temperatures were less than their volume phase transition temperatures. The SANS data were fitted using a model which consisted of Porod and Ornstein-Zernike form factors. The analysis showed that the macroscopic hydrodynamic diameter of the microgel particles and the submicroscopic mesh size of the network are linearly related. This is the first study to demonstrate affine swelling for poly(NIPAM/xBA) microgels. Furthermore, the mesh size does not appear to be strongly affected by x. The data suggest that the swollen particles have a mostly homogeneous structure, although evidence for a thin, low segment density shell is presented. The study confirms that poly(NIPAM/xBA) microgel particles have a core-shell structure. The shell has an average thickness of approximately 20 nm for poly(NIPAM/1BA) particles which appears to be independent of temperature over the range studied. The analysis suggests that the particles contained approximately 50 vol % water at 50 degrees C. The molar mass of the poly(NIPAM/1BA) microgel particles was estimated as 6 x 10(9) g mol(-1).     

Mononuclear rearrangement of heterocycles in zwitterionic micelles of amine oxide surfactants

The pH-induced swelling of poly(2-vinylpyridine) microgel particles was studied using dynamic light scattering. The increase in particle diameter with decreasing pH was modeled using a well-established thermodynamic model for microgel swelling. The Maxwell construction was applied to extend the model and yield a prediction for a pH-responsive microgel across the entire pH range. The model predicts a first order phase transition for polymer-solvent combinations with a Flory interaction parameter, χ, greater than a critical value χ(c). The modified theory compared favorably to the dynamic light scattering data for the hydrodynamic diameter of microgel particles based on 2-vinylpyridine at different pH values. In particular, the swelling transition is both predicted theoretically and observed experimentally to occur at a pH lower than the pK(a) of the polymer.     

Investigating the temperature dependence of the viscosity of a non-Newtonian fluid within lithographically defined microchannels

We present a study of the rheological phenomenology of a non-Newtonian glass former within hybrid microchannels above the vitrification region. We determined the temperature behavior of the viscosity, which is well fitted by a Vogel-Fulcher-Tamman law for shear rates between 4 x 10(-2) and 9 x 10(-1) s(-1). The microflow viscosity was compared with previously reported conductivity data of the investigated molecular system. Our findings provide an insight into the coupling between the structural dynamics in the bulk and that within the microchannels, suggesting lithographically defined microfluidic systems as promising tools for the investigation of the rheological properties of complex liquids.     

Efficient synthesis of sterically stabilized pH-responsive microgels of controllable particle diameter by emulsion polymerization

Emulsion polymerization of 2-vinylpyridine (2VP) in the presence of divinylbenzene (DVB) cross-linker, a cationic surfactant, and a hydrophilic macromonomer, monomethoxy-capped poly(ethylene glycol) methacrylate (PEGMA), at around neutral pH and 60 degrees C afforded near-monodisperse, sterically stabilized latexes at approximately 10% solids. Judicious selection of the synthesis parameters enabled the mean latex diameter to be varied over an unusually wide range for one-shot batch syntheses. Scanning electron microscopy studies confirmed near-monodisperse spherical morphologies, with mean weight-average particle diameters ranging from 370 to 970 nm depending on the initiator, polymeric stabilizer, and surfactant concentrations. Particle sizing studies were also conducted using disk centrifuge photosedimentometry and dynamic light scattering and gave similar data. These lightly cross-linked latexes acquired cationic microgel character at low pH, as expected. The critical pH for this latex-to-microgel transition was around pH 4.1 at 1.0 wt % DVB, which is significantly lower than the pKa of 4.92 estimated for linear P2VP homopolymer by acid titration. 1H NMR and aqueous electrophoresis studies indicated that substantial swelling occurred at low pH due to protonation of the 2VP groups, while dynamic light scattering (DLS) studies indicated volumetric swelling ratios of up to 3 orders of magnitude, depending on the initial latex diameter. Systematic variation of the degree of cross-linking led to a monotonic decrease in the pKa values of the P2VP latexes (as judged by acid titration) and also the critical swelling pH (as judged by visual inspection). This was attributed to the increasingly branched nature of the P2VP chains in their swollen microgel form. Preliminary studies of the kinetics of acid-induced swelling were also conducted using the pH jump method in conjunction with a stopped-flow apparatus. These P2VP latexes swell significantly faster than P2VP latexes described in the literature and the characteristic time scales observed in the present study are much closer to those predicted by the Tanaka equation.     

Phase separation and rheological behavior in thermoplastic modified epoxy systems

The relationship between rheological behavior and phase separation in polyesterimide modified epoxy systems was studied by rheometry, time-resolved light scattering (TRLS), and Differential Scanning Calorimetry (DSC). The rheological behaviors of blends during phase separation showed an exponential grow of complex viscosity, while the phase separation was inhibited by the vitrification of the polyesterimide-rich matrix phase rather than gelation of dispersed epoxy-rich particles. The characteristic relaxation time obtained by the simulation of complex viscosity could be described well by the Williams–Landel–Ferry equation, which corresponded well with the light scattering results. Therefore, this work would further provide the experimental proofs that the exponential relaxation behavior of complex viscosity could be attributed to the viscoelastic flow of epoxy-rich escaping from polyesterimide-rich matrix during phase separation.     

聚(N-异丙基丙烯酰胺)水凝胶微球体积相变的研究

窄分散的聚（Ｎ 异丙基丙烯酰胺）水凝胶微球用乳液聚合方法制备，并用动态和静态光散射对其体积相变进行了研究．与水中聚（Ｎ 异丙基丙烯酰胺）线性单链比较，水中凝胶微球的体积相变温度较高，对温度的响应比较平缓．相变是连续的，有别于大块凝胶非连续的体积变化．在体积相变过程中，凝胶微球始终是密度均一的热力学稳定球体．从相变过程网络密度的变化可以确定，绝大部分的水在收缩过程被排了出来，但在紧缩的凝胶微球中仍含有约７０％的水．     

Synthesis and characterization of thermoreversible biopolymer microgels based on hydrogen bonded nucleobase pairing

We describe the synthesis and characterization of a thermoreversibly cross-linked biopolymer microgel based on protein, DNA, and peptide nucleic acid (PNA) components. The DNA assembles into a trifunctional three-way junction (TWJ) with single-stranded overhangs. PNA oligomers complementary to these overhangs and bearing terminal biotin groups hybridize to the DNA TWJ and simultaneously bind to the tetrafunctional protein avidin, leading to a cross-linked system. Dynamic light scattering experiments reveal that micron-sized particles are formed. Static light scattering was used to characterize the internal structure of these microgels, which were found to have a fractal dimension of 1.85, indicative of a loose network structure. Heating disrupts the weakest component in the system, namely the PNA-DNA hybrid, resulting in dissolution of the microgel, while cooling restores the hydrogen bonding leading to reassembly of the microgel. Variation of the nucleotide sequence permits tuning of the gelation temperature with fine control.