Fibrillar Structure of Methylcellulose Hydrogels

It is well established that aqueous solutions of methylcellulose (MC) can form hydrogels on heating, with the rheological gel point closely correlated to the appearance of optical turbidity. However, the detailed gelation mechanism and the resulting gel structure remain poorly understood. Herein the fibrillar structure of aqueous MC gels was precisely quantified with a powerful combination of (real space) cryogenic transmission electron microscopy (cryo-TEM) and (reciprocal space) small-angle neutron scattering (SANS) techniques. The cryo-TEM images reveal that MC chains with a molecular weight of 300 000 g/mol associate into fibrils upon heating, with a remarkably uniform diameter of 15 ± 2 nm over a range of concentrations. Vitrified gels also exhibit heterogeneity in the fibril density on the length scale of hundreds of nanometers, consistent with the observed optical turbidity of MC hydrogels. The SANS curves of gels exhibit no characteristic peaks or plateaus over a broad range of wavevector, <i>q</i>, from 0.001–0.2 Å^–1. The major feature is a change in slope from <i>I</i> ∼ <i>q</i>^–1.7 in the intermediate <i>q</i> range (0.001 – 0.01 Å^–1) to <i>I</i> ∼ <i>q</i>^–4 above <i>q</i> ≈ 0.015 Å^–1. The fibrillar nature of the gel structure was confirmed by fitting the SANS data consistently with a model based on the form factor for flexible cylinders with a polydisperse radius. This model was found to capture the scattering features quantitatively for MC gels varying in concentration from 0.09–1.3 wt %. In agreement with the microscopy results, the flexible cylinder model indicated fibril diameters of 14 ± 1 nm for samples at elevated temperatures. This combination of complementary experimental techniques provides a comprehensive nanoscale depiction of fibrillar morphology for MC gels, which correlates very well with macro-scale rheological behavior and optical turbidity previously observed for such systems

Linear and Nonlinear Rheological Behavior of Fibrillar Methylcellulose Hydrogels

Cryogenic transmission electron microscopy and small-angle neutron scattering recently have revealed that the well-known thermoreversible gelation of methylcellulose (MC) in water is due to the formation of fibrils, with a diameter of 15 ± 2 nm. Here we report that both the linear and nonlinear viscoelastic response of MC solutions and gels can be described by a filament-based mechanical model. In particular, large-amplitude oscillatory shear experiments show that aqueous MC materials transition from shear thinning to shear thickening behavior at the gelation temperature. The critical stress at which MC gels depart from the linear viscoelastic regime and begin to stiffen is well predicted from the filament model over a concentration range of 0.18–2.0 wt %. These predictions are based on fibril densities and persistence lengths obtained experimentally from neutron scattering, combined with cross-link spacings inferred from the gel modulus via the same model

Gelation, Phase Separation, and Fibril Formation in Aqueous Hydroxypropylmethylcellulose Solutions

The thermoresponsive behavior of a hydroxy­propyl­methyl­cellulose (HPMC) sample in aqueous solutions has been studied by a powerful combination of characterization tools, including rheology, turbidimetry, cryogenic transmission electron microscopy (cryoTEM), light scattering, small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS). Consistent with prior literature, solutions with concentrations ranging from 0.3 to 3 wt % exhibit a sharp drop in the dynamic viscoelastic moduli <i>G</i>′ and <i>G</i>″ upon heating near 57 °C. The drop in moduli is accompanied by an abrupt increase in turbidity. All the evidence is consistent with this corresponding to liquid–liquid phase separation, leading to polymer-rich droplets in a polymer-depleted matrix. Upon further heating, the moduli increase, and <i>G</i>′ exceeds <i>G</i>″, corresponding to gelation. CryoTEM in dilute solutions reveals that HPMC forms fibrils at the same temperature range where the moduli increase. SANS and SAXS confirm the appearance of fibrils over a range of concentration, and that their average diameter is ca. 18 nm; thus gelation is attributable to formation of a sample-spanning network of fibrils. These results are compared in detail with the closely related and well-studied methylcellulose (MC). The HPMC fibrils are generally shorter, more flexible, and contain more water than with MC, and the resulting gel at high temperatures has a much lower modulus. In addition to the differences in fibril structure, the key distinction between HPMC and MC is that the former undergoes liquid–liquid phase separation prior to forming fibrils and associated gelation, whereas the latter forms fibrils first. These results and their interpretation are compared with the prior literature, in light of the relatively recent discovery of the propensity of MC and HPMC to self-assemble into fibrils on heating