Aqueous solutions of hydroxypropyl methylcellulose (HPMC) show inverse thermoreversible gelation, i.e., they respond to small temperature variations exhibiting sol–gel transition during heating, and reversibly gel–sol transition during cooling. According to the pertinent literature on HPMC aqueous systems, at room temperature, the loss modulus (G”) is higher than the storage modulus (G’). During the heating ramp, the viscoelastic response follows a peculiar path: initially, G” and G’ smoothly decrease, then drop to a minimum and finally increase. Eventually, G’ overcomes G”, indicating the gel formation. A recent explanation of this behaviour considers a two-step mechanism: first, phase separation occurs, then fibrils form from a polymer-rich phase and entangle, leading to a three-dimensional network. Based on this, our research focuses on the rheological analysis of the different steps of the sol–gel transition of an HPMC aqueous solution. We perform different viscoelastic tests: thermal ramps, time sweeps, and frequency sweeps at selected characteristic temperatures. We couple classical analysis of the SAOS experiments with an innovative approach based on the evaluation of the activation energy (Ea), made possible by the instrument intrinsic temperature oscillations around the target value. Results show that Ea can be a valid tool that contributes to further clarifying the peculiar microstructural evolution occurring in this kind of thermoreversible gel.

During enhanced oil recovery (EOR), reservoir heterogeneities and fluids distributions promote preferential flow channels formation. Therefore, different types of gels have been proposed to improve swept efficiency on chemical flooding by plugging high permeability zones. The purpose of this article is to evaluate the effect that nanotechnology has on the inhibition of syneresis and the rheological properties of the Acrylamide Sodium Acrylate Copolymer/Chromium (III) Acetate gel system for conformance applications in mature reservoirs. Thus, a methodology is proposed in four stages: First, (I) nanoparticles synthesis, and characterization, followed by (II) bottle tests to monitor gelation kinetics and syneresis degree at 70 °C, then (III) description of the rheological evaluation on static and dynamic conditions to calculate gelation time and viscoelastic modulus (G’ and G”), and finally (IV) the displacement test with the best gel system in the presence of nanoparticles. Results showed that the best nanoparticle was the chromium oxide (Cr₂O₃), which represented the lesser syneresis degree and increased gelation time. Syneresis of gel samples in the presence of Cr₂O₃ at day 30 was under 1% for gels prepared with 4000, 6000, and 8000 mg·L⁻¹ of polymer, and polymer to crosslinker ratio (p/c) of 40:1. Regarding SiO₂, MgO, and Al₂O₃ nanoparticles, results show an improvement of gel strength. However, their thermal stability in terms of syneresis was lower. Displacement test in a triple parallel Slim Tube was able to recover an additional 37% of oil of the total oil present in the sandpacks, confirming the effectivity of the system when 100 mg·L⁻¹ of Cr₂O₃ nanoparticles are included.

We study the shear rheological behavior of a commercial stereolithography paste containing ≈50 vol. % of zirconia particles (diameter ≈ 100 nm) with the aim to clarify physical mechanisms occurring during the “scraping” step of this yield stress fluid. Beyond a flow curve characterized by a high zero-shear viscosity accompanied with an overall shear-thinning behavior, we investigate in a systematic way the transient regime through start-up experiments. We demonstrate that a structural transition occurs between 10−2 and 10−1 s−1, resulting in an apparent interruption of the shear-thinning. The corresponding transient response presents a pronounced extra-growth of the shear stress before to stabilize at high strain amplitude and a negative first normal stress difference peak, both effects become stronger at higher shear rates. These observations are rationalized based on the high interparticle friction owing to the polyhedral shape and the roughness of the particles. In addition, relaxation tests following the start-up experiments reveal that the samples submitted to shear rates higher than 10−1 s−1 cannot relax the shear stress to the same level as in low shear rate experiments, suggesting a durable structural modification likely to impact the quality of the parts prior to their debinding and densification. Finally, we utilize orthogonal superposition rheology to illustrate how the application of an oscillatory deformation during the scraping procedure could help to reduce the shear-thinning interruption and improve the stereolithography processing as already observed empirically during scraping.

Hydroxypropyl methylcellulose (HPMC) is a polymer made of a cellulose backbone with etherified methoxy and hydroxypropyl substitutions that undergoes a reversible inverse thermo‐gelation upon heating. The thermo‐gelation follows a two‐step mechanism: first, phase separation occurs, then fibrils, formed in the polymer‐rich phase, entangle to form the three‐dimensional gel network. This work aims at understanding the influence of degree (DS) and molar substitution (MS) on the thermo‐gelation process. DS is the number of methyl groups, and the MS is the hydroxypropyl content per anhydroglucose unit. The thermo‐gelation process is here rheologically investigated for two HPMC samples, which have similar molecular weight but different MS and DS: thermal ramps are coupled with time sweep tests at selected temperatures and with frequency sweep experiments. Results show an important effect not only on the transition temperatures (beginning of the phase separation, beginning of the gelation) but also on the kinetics of the different phases of the process.