Erik Geissler

Structure of swollen polydimethyl siloxane gels

Light and small angle neutron scattering results are presented for a series of poly(dimethyl siloxane) (PDMS) gels, cured in the dry state by endlinking with a trifunctional crosslinking agent, ethyl triacetoxy silane (ETAS). For gels swollen in octane, the scattered light and the smallest angle neutron response are dominated by scattering from aggregates of polymerized ETAS, the mean radius of which was found in this system to be ∼800 A, and which have a smooth surface in the length scale between 500 and 100 A. The internal surface area of this precipitate was roughly 200 cm2 per cm3 of the swollen gel. Only about one third of the free ETAS participates in this condensed phase. The rest is disseminated as oligomers or monomers throughout the gel. The gel itself appears as a solution‐like structure with in addition permanent waves in the polymer concentration distribution. In this system, the permanent waves could be modeled by a Gaussian function of characteristic width ΔR=80 A and relative amplitude 〈Δc...

DLS and SAXS investigations of organic gels and aerogels

Abstract Recent investigations have shown that the structure of organic aerogels can be significantly modified by changing the precursors, the solvent and the nature of the catalyst involved in the sol–gel reaction. It is therefore highly desirable to investigate the sol–gel mechanism. For this purpose, dynamic light scattering (DLS) measurements have been performed at different stages of the reaction for base- or acid-catalyzed gelation of resorcinol–formaldehyde (RF) using water or acetone as solvents. The structure of aged gels was investigated by small-angle X-ray scattering (SAXS) and compared to that of the aerogels obtained after exchange of solvent by supercritical CO2 and drying of the aged gels. It is shown that acid-catalyzed gelation of RF in acetone can be described by percolation, which explains that this series of aerogels consists of mass fractal aggregates (Dm=2.5). The partial collapse of this polymeric gel yielding colloidal particles in the aerogel can be attributed to deswelling in supercritical CO2. DLS indicates that gelation of RF with a base catalyst yields a colloidal gel whose structure remains practically unchanged in the aerogel, as shown by SAXS.

Anomalous small angle x-ray scattering determination of ion distribution around a polyelectrolyte biopolymer in salt solution.

The distribution of counterions in solutions of high molecular mass hyaluronic acid, in near-physiological conditions where mono- and divalent ions are simultaneously present, is studied by small angle neutron scattering and anomalous small angle x-ray scattering. The solutions contain either sodium or rubidium chloride together with varying concentrations of calcium or strontium chloride. The effects of monovalent-divalent ion exchange dominate the amplitude and the form of the counterion cloud. In the absence of divalent ions, the shape of the anomalous scattering signal from the monovalent ions is consistent with the distribution calculated from the Poisson-Boltzmann equation, as found by other workers. In mixtures of monovalent and divalent ions, however, as the divalent ion concentration increases, both the diameter and the amplitude of the monovalent ion cloud decrease. The divalent counterions always occupy the immediate neighborhood of the charged polyanion. Above a given concentration their anomalous scattering signal saturates. Even in a large excess of divalent ions, ion exchange is incomplete.

Ions in hyaluronic acid solutions

Hyaluronic acid (HA) is an anionic biopolymer that is almost ubiquitous in biological tissues. An attempt is made to determine the dominant features that account for both its abundance and its multifunctional role, and which set it apart from other types of biopolymers. A combination of osmotic and scattering techniques is employed to quantify its dynamic and static properties in near-physiological solution conditions, where it is exposed both to mono- and divalent counterions. An equation of state is derived for the osmotic pressure Pi in the semidilute concentration region, in terms of two variables, the polymer concentration c and the ionic strength J of the added salt, according to which Pi=1.4x10(3)c(9/4)/J(3/4) kPa, where c and J are expressed in mole. Over the physiological ion concentration range, the effect of the sodium chloride and calcium chloride on the osmotic properties of HA solutions is fully accounted for by their contributions to the ionic strength. The absence of precipitation, even at high CaCl(2) concentrations, distinguishes this molecule from other biopolymers such as DNA. Dynamic light scattering measurements reveal that the collective diffusion coefficient in HA solutions exceeds that in aqueous solutions of typical neutral polymers by a factor of approximately 5. This property ensures rapid adjustment to, and recovery from, stress applied to HA-containing tissue. Small angle x-ray scattering measurements confirm the absence of appreciable structural reorganization over the observed length scale range 10-1000 A, as a result of calcium-sodium ion exchange. The scattered intensity in the transfer momentum range q>0.03 A(-1) varies as 1/q, indicating that the HA chain segments in semidilute solutions are linear over an extended concentration range. The osmotic compression modulus c partial differential Pi/partial differential c, a high value of which is a prerequisite in structural biopolymers, is several times greater than in typical neutral polymer solutions.

Experimental evidence for two thermodynamic length scales in neutralized polyacrylate gels

The small angle neutron scattering (SANS) behavior of fully neutralized sodium polyacrylate gels is investigated in the presence of calcium ions. Analysis of the SANS response reveals the existence of three characteristic length scales, two of which are of thermodynamic origin, while the third length is associated with the frozen-in structural inhomogeneities. This latter contribution exhibits power law behavior with a slope of about −3.6, reflecting the presence of interfaces. The osmotically active component of the scattering signal is defined by two characteristic length scales, a correlation length ξ and a persistence length L.

Gel-like behavior in aggrecan assemblies

Aggrecan, a large biological polyelectrolyte molecule with a bottlebrush shape, forms complexes with hyaluronic acid (HA) that provide compressive resistance in cartilage. In solutions of aggrecan alone, the concentration dependence of the osmotic pressure Pi is marked by self-assembly of the molecules into aggregates. When HA is added to the solution at low aggrecan concentration c, the osmotic pressure is reduced, but in the physiological concentration range this trend is reversed. The osmotic modulus c partial differentialPi partial differentialc, which determines load bearing resistance, is enhanced in the HA-containing solutions. Dynamic light scattering (DLS) measurements show that the aggregates behave like microgels and that they become denser as the aggrecan concentration increases. The degree of densification is greatest at large distance scales in the microgels, but decreases at short distance scales. Measurements at higher resolution, involving small angle neutron scattering and small angle x-ray scattering (SAXS), confirm that at length scales shorter than 1000 angstroms, the density is independent of the concentration and that the individual bottlebrushes in the microgels retain their identity. The absence of collective diffusion modes in the relaxation spectrum, measured by DLS and neutron spin echo, corroborates the lack of interpenetration among the aggrecan subunits in the microgel. Complexation with HA modifies the long-range spatial organization of the microgels. Comparison of the scattering pattern of the individual aggrecan molecules obtained from SAXS measurements with that of the complexes measured by DLS shows that the aggrecan-HA structure is denser and is more uniform than the random microgels. This enhanced space-filling property allows higher packing densities to be attained, thus, optimizing resistance to osmotic compression.

Microphase Structure of Poly(N-isopropylacrylamide) Hydrogels As Seen by Small- and Wide-Angle X-ray Scattering and Pulsed Field Gradient NMR

Above the lower critical solution temperature T(c) (ca. 34 degrees C), poly(N-isopropylacrylamide) hydrogels become weakly hydrophobic and undergo microphase separation. Macroscopic deswelling, however, is extraordinarily slow, the out-of equilibrium state of the gel being conserved for many days. In this article the structure of the microphase-separated state above T(c) is probed by small-angle X-ray scattering and by pulsed field gradient NMR of the protons of water, both in the water phase and in the polymer-rich phase. Above T(c) the gel comprises two microphases, separated by smooth interfaces. The cavities occupied by the water phase form a connected network. The diffusion rate of the water molecules in this phase varies from one cavity to another and can be described by a Gaussian distribution. Water molecules belonging to the polymer-rich phase are also mobile, but their self-diffusion coefficient D is greatly diminished. Absence of compartmentalization of the water phase implies that the slow deswelling rate of the gel is not due to trapping of the water phase.

Scattering from dilute ferrofluid suspensions in soft polymer gels

Small angle neutron and x-ray scattering methods are used to investigate the structure of dilute suspensions of two different ferrofluid systems dispersed in soft polyacrylamide hydrogels. It is found that the particles in the fluid are fractal aggregates composed of smaller particles of radius ca. 5 nm. The fractal dimension is strongly dependent on sample, taking the value 1.7 in the first sample and 2.9 in the second sample. In the presence of a magnetic field the aggregates orient, but are restricted in both their translational and rotational freedom. The effect of the gel elasticity is treated as a hindrance to the orientation process.

Swelling of neutralized polyelectrolyte gels

Abstract Measurements are reported of the swelling pressure ω and of the collective diffusion coefficient D c in two series of salt-free neutralized polyelectrolyte gels, one a poly(acrylamide–acrylic acid) copolymer, the other cross-linked potassium polyacrylic acid. The values of D c measured by macroscopic deswelling are in reasonable agreement with those measured by dynamic light scattering. D c increases as the degree of swelling of the gel increases, with similar behaviour being found for the elastic modulus G . The osmotic pressure, Π = ω + G , displays a power law behaviour over the concentration range explored, the exponent σ depending on the counter-ion concentration: σ ≈1 for the sample of lower charge density, while for the sample with a high charge density, σ ≈1.5. The latter behaviour, unexpected at low polymer concentrations, is interpreted in terms of the inequivalence between static and dynamic concentration fluctuations.

Cu-doped resorcinol-formaldehyde (RF) polymer and carbon aerogels.

Introduction of transition metal salt(s) onto the surface of porous carbons may increase the selectivity and/or efficiency of these adsorbents in catalysis or separation. Carbon aerogels with low pressure drop are particularly suited for these applications. Moreover the sol-gel process used in the synthesis of the resorcinol-formaldehyde polymer gel (RF) precursors offers an extra opportunity for introducing metal ions. Salts of different metals modify both the macroscopic texture and the porosity, depending on the synthesis protocol. In this paper we show, by means of low temperature nitrogen adsorption measurements and SEM, as well as small- and wide-angle X-ray scattering (SAXS and WAXS), how the addition of copper acetate at three different stages influences not only the specific surface area but also the resulting overall structure over a wide range of length scales. Posttreatment in either the polymer or the carbon aerogel stage provides a means of adjusting the copper content. While the Cu-containing carbon aerogels differ mainly in their micropore volume but not in the width of the distribution, their pore size window in the mesopore range can be tuned between 50 and 400 A by the protocol of Cu addition. The synthesis protocol also determines the chemical form of the copper.