Supramolecular dynamic binary complexes with pH and salt-responsive properties for use in unconventional reservoirs

Hydraulic fracturing of unconventional reservoirs has seen a boom in the last century, as a means to fulfill the growing energy demand in the world. The fracturing fluid used in the process plays a substantial role in determining the results. Hence, several research and development efforts have been geared towards developing more sustainable, efficient, and improved fracturing fluids. Herein, we present a dynamic binary complex (DBC) solution, with potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure formed by the self-assembly of low molecular weight viscosifiers (LMWVs) oleic acid and diethylenetriamine into an elongated entangled network under alkaline conditions. With less than 2 wt% constituents dispersed in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. Key features include responsiveness to pH and salinity, and a zero-shear viscosity that could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were more pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time. In conclusion, this DBC solution system has potential to be utilized as a smart salt-responsive, pH-switchable hydraulic fracturing fluid.

Controlled Degradation of Commercial Resin for Meltblown Nonwoven Fabric Sheet Production

Manufacturing meltblown nonwoven fabrics requires special grades of resin with very low viscosity, which are not dealt with so much on market and cost quite high compared to the standard grades. We propose a high-shear rate processing method that can quickly and easily produce such low-viscosity resin from the commercial one without using organic peroxides. In this method, we apply high-shear stress to molten resin by using a high-shear extruder, which is a single screw extruder with high screw rotation speed, and the resin is thermally decomposed of its shear-induced heat which is quickly generated. We found that polypropylene with a value of melt flow rate over a thousand, which was required for the meltblown process, was produced from the standard grade with the high-shear extruder at the screw rotation speed of 3600 min−1 and the barrel temperature over 300 ∘C. Using the degradated polypropylene, a meltblown nonwoven fabric sheet was successfully fabricated. We also developed a numerical simulator of the high-shear extruder which can handle a wide range of the screw rotation speed and barrel temperature by the Nusselt number modulated with the operational conditions. The experimental values of the zero-shear viscosity and temperature at the exit of the extruder agreed well with the simulation results. Our high-shear rate processing method will enable us to quickly and easily produce various meltblown nonwoven fabric sheets at low costs.

Influence of rheological characteristics on the quality of 3D printing of food pastes

In extrusion 3D printing, the rheological properties of food are critical to achieving quality printing. The aim of this study is to investigate potential correlations between the printability of food pastes and rheological characteristics. Potato and tomato puree were used as a model system. The rheological properties of mashed potatoes with the addition of potato starch and their behavior during 3D printing have been investigated. A correlation has been established between the formulation and manufacturability in 3D printing. Potato mass without starch had a low yield point, which affected the deformation and subsidence of the mass later. At the same time, the addition of 2% starch showed excellent extrudability and printability, that is, the ability to flow. Under these conditions, the printed objects had a smooth shape, good resolution, and could withstand shape over time. The object with the addition of 4% starch represented good shape retention but poor extrudability due to its high consistency index and toughness. The results obtained using tomato puree showed a linear correlation between ingredient flow stress, zero shear viscosity and corresponding print stability. The extrusion pressure required to extrude tomato paste increases linearly with increasing flow voltage. Modules of viscosity, elasticity, and zero shear rate turned out to be not linearly correlated with the extrusion force, which can be explained by the fact that these parameters reflect the rheological properties of the non-deforming state of the material, in contrast to the flow stresses.

The Influence of Zero Shear Viscosity of TLA-Modified Binder and Mastic Composition on the Permanent Deformation Resistance of Mastic Asphalt Mixture

Mastic asphalt (MA) has been particularly popular in recent years for bridge pavements due to many advantages such as easy application, good waterproofing properties, and high durability. However, the drawback of mastic asphalt in comparison to other asphalt mixtures is its lower resistance to permanent deformation. Trinidad Lake Asphalt (TLA) is often applied to make mastic asphalt resistant to permanent deformation. Practical experience demonstrates that serious failures may occur if MA pavement design and materials selection is not taken into account sufficiently. Therefore in this study, the influence of two parameters: zero shear viscosity (ZSV) of TLA-modified binder and mastic composition described by the filler–binder ratio, on the permanent deformation resistance of the MA mixture was evaluated. The primary purpose of determining the ZSV of the TLA-modified binders was to evaluate the rutting potential of the binders. The permanent deformation (rutting) resistance of the MA mixtures was evaluated based on static and dynamic indentation tests. The optimum content of TLA in the base bitumen and the optimum filler–binder ratio in the MA mixture were obtained based on multiple performance evaluations for modified binder, mastic and MA mixtures, i.e., 20% and 4.0, respectively.

Investigation of rheological properties of asphalt emulsions

Rheology is critical issue in the workability, stabilization and engineering performance of asphalt emulsions. The objective of this study is to investigate the rheological properties of asphalt emulsions. To achieve this goal, a preshear protocol was introduced and four kinds of asphalt emulsions were tested base on preshear. Firstly, the necessarity of preshear was analyzed and the suitable range of preshear rate and preshear time of the studied asphalt emulsions were given. Then, the rheological properties of asphalt emulsions were studied after preshear. Finally, the palierne model was modified and the storage/loss modulus of asphalt emulsions was accurately predicted by the modified palierne model. The results showed that it’s necessary to preshear asphalt emulsions before testing rheological properties. The viscosity, zero shear viscosity, storage and loss modulus of asphalt emulsions increase with the increase in solid content. The prediction results of the modified palierne model are better than that of palierne model. The storage/loss modulus of asphalt emulsions can be effectively predicted by the modified palierne model. This study has considerable meaning to the promotion of production and manufacturing of asphalt emulsions.

Viscoelastic and Deformation Characteristics of Structurally Different Commercial Topical Systems

Rheological characteristics and shear response have potential implication in defining the pharmaceutical equivalence, therapeutic equivalence, and perceptive equivalence of commercial topical products. Three creams (C1 and C3 as oil-in-water and C2 as water-in-oil emulsions), and two gels (G1 and G2 carbomer-based) were characterized using the dynamic range of controlled shear in steady-state flow and oscillatory modes. All products, other than C3, met the Critical Quality Attribute criteria for high zero-shear viscosity (η0) of 2.6 × 104 to 1.5 × 105 Pa∙s and yield stress (τ0) of 55 to 277 Pa. C3 exhibited a smaller linear viscoelastic region and lower η0 (2547 Pa∙s) and τ0 (2 Pa), consistent with lotion-like behavior. All dose forms showed viscoelastic solid behavior having a storage modulus (G′) higher than the loss modulus (G″) in the linear viscoelastic region. However, the transition of G′ > G″ to G″ > G′ during the continual strain increment was more rapid for the creams, elucidating a relatively brittle deformation, whereas these transitions in gels were more prolonged, consistent with a gradual disentanglement of the polymer network. In conclusion, these analyses not only ensure quality and stability, but also enable the microstructure to be characterized as being flexible (gels) or inelastic (creams).

pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants

Surfactant aggregates have long been considered as a tool to improve drug delivery and have been widely used in medical products. The pH-responsive aggregation behavior in anionic gemini surfactant 1,3-bis(N-dodecyl-N-propanesulfonate sodium)-propane (C12C3C12(SO3)2) and its mixture with a cationic monomeric surfactant cetyltrimethylammonium bromide (CTAB) have been investigated. The spherical-to-wormlike micelle transition was successfully realized in C12C3C12(SO3)2 through decreasing the pH, while the rheological properties were perfectly enhanced for the formation of wormlike micelles. Especially at 140 mM and pH 6.7, the mixture showed high viscoelasticity, and the maximum of the zero-shear viscosity reached 1530 Pa·s. Acting as a sulfobetaine zwitterionic gemini surfactant, the electrostatic attraction, the hydrogen bond and the short spacer of C12C3C12(SO3)2 molecules were all responsible for the significant micellar growth. Upon adding CTAB, the similar transition could also be realized at a low pH, and the further transformation to branched micelles occurred by adjusting the total concentration. Although the mixtures did not approach the viscosity maximum appearing in the C12C3C12(SO3)2 solution, CTAB addition is more favorable for viscosity enhancement in the wormlike-micelle region. The weakened charges of the headgroups in a catanionic mixed system minimizes the micellar spontaneous curvature and enhances the intermolecular hydrogen-bonding interaction between C12C3C12(SO3)2, facilitating the formation of a viscous solution, which would greatly induce entanglement and even the fusion of wormlike micelles, thus resulting in branched microstructures and a decline of viscosity.

Impact of Graphene Oxide on Zero Shear Viscosity, Fatigue Life and Low-Temperature Properties of Asphalt Binder

This study has investigated the impact of graphene oxide (GO) in enhancing the performance properties of an asphalt binder. The control asphalt binder (60/70 PEN) was blended with GO in contents of 0%, 0.5%, 1%, 1.5%, 2%, and 2.5%. The permanent deformation behavior of the modified asphalt binders was evaluated based on the zero shear viscosity (ZSV) parameter through a steady shear test approach. Superpave fatigue test and the linear amplitude sweep (LAS) method were used to evaluate the fatigue behavior of the binders. A bending beam rheometer (BBR) test was conducted to evaluate the low-temperature cracking behavior. Furthermore, the storage stability of the binders was investigated using a separation test. The results of the ZSV test showed that GO considerably enhanced the steady shear viscosity and ZSV value, showing a significant contribution of the GO to the deformation resistance; moreover, GO modification changed the asphalt binder’s behavior from Newtonian to shear-thinning flow. A notable improvement in fatigue life was observed with the addition of GO to the binder based on the LAS test results and Superpave fatigue parameter. The BBR test results revealed that compared to the control asphalt, the GO-modified binders showed lower creep stiffness (S) and higher creep rate (m-value), indicating increased cracking resistance at low temperatures. Finally, the GO-modified asphalt binders exhibited good storage stability under high temperatures.

Effects of Aging on the Physical and Rheological Properties of Trinidad Lake Asphalt Modified Bitumen

The application of various modifiers has emerged in recent years to improve conventional petroleum-based bitumen properties. The natural asphalt called Trinidad Lake Asphalt (TLA) has been applied very often due to its consistent properties, high viscosity and density, and superior rheological properties, and effective blending with other bitumen. However, most studies on TLA-modified binders always focused on physical and rheological properties in the original (unaged) condition, but the details about aging properties are often neglected. This study aimed to investigate the effect of short-term aging on the physical and rheological characteristics of the 35/50 base bitumen modified by the addition of two different TLA contents. The conventional physical tests and dynamic shear rheological tests were undertaken before and after aging to measure the penetration and softening point, complex shear modulus, and phase angle of the modified binders, as well as to calculate the zero shear viscosity using the Cross model fitting procedure. Based on the results of the above-mentioned comprehensive testing, the effect of aging on TLA-modified binder properties was evaluated using aging indices, as well as a direct comparison of results. The tests revealed that the short-term aging of TLA-modified binders did not worsen or reduce the pavement resistance to permanent deformation or the load-bearing capacity of the asphalt mixture.