Search Results (13)

Managing excessive water production in oil fields during primary, secondary, or enhanced recovery remains challenging. It increases costs and reduces hydrocarbon recovery, particularly in reservoirs with high-conductivity pathways such as high-permeability zones and fractures. Hydrogels are commonly used for water blocking and retention; however, their effectiveness diminishes at higher flow rates due to mechanical weaknesses and structural limitations. These problems are intensified under harsh environmental conditions, including high temperatures, salinity, and hardness. In this study, we investigate how altering the molecular suprastructure of preformed particle gel (PPG) can improve its effectiveness in shear-responsive water-blockage treatments, particularly when traditional PPGs cannot control rising flow rates. We enhance the shear-responsive mechanical properties of a composite PPG by increasing the density and diversity of intermolecular interactions. We use two different strategies: first, incorporating cationic groups into the polymer backbone to form a polyampholyte network with stronger electrostatic interactions; second, adding a linear anionic polymer to generate a secondary interpenetrating network that can undergo a coil–stretch transition under thermal and shear stimuli, thereby enhancing its own solvation and whole-network expansion. Molecular simulations provide an interpretation of the experimentally observed shear-thickening response and enhanced disproportionate permeability reduction at high flow rates. The water residual resistance factor of the improved PPGs deviates from the typical shear-thinning power-law behavior (n < 1) observed in conventional PPG, showing shear-thickening (n > 1). Tests reveal a strong ability to preferentially reduce water flow over oil, with Disproportionate Permeability Reduction increasing from 8 to 117 in the high-flow-rate zone. The enhanced strength and thermal stability also improve resistance to washout under high-pressure gradients. This research provides a novel approach to tailoring the microscopic architecture of PPGs to achieve selective, robust water blockage, offering a high-efficiency solution for complex reservoir environments. Full article

Polyampholytes combine cationic and anionic groups in one macromolecular platform and are emerging as versatile components for energy storage and conversion. This review synthesizes how their charge balance, hydration, and architecture can be engineered to address ionic transport, interfacial stability, and safety across batteries, supercapacitors, solar cells, and fuel cells. We classify annealed, quenched, and zwitterionic systems, outline molecular design strategies that tune charge ratio, distribution, and crosslinking, and compare device roles as gel or solid electrolytes, eutectogels, ionogels, binders, separator coatings, and interlayers. Comparative tables summarize ionic conductivity, cation transference number, electrochemical window, mechanical robustness, and temperature tolerance. Across Li and Zn batteries, polyampholytes promote ion dissociation, homogenize interfacial fields, suppress dendrites, and stabilize interphases. In supercapacitors, antifreeze hydrogels and poly(ionic liquid) networks maintain conductivity and elasticity under strain and at subzero temperature. In solar cells, zwitterionic interlayers improve work function alignment and charge extraction, while ordered networks in fuel cell membranes enable selective ion transport with reduced crossover. Design rules emerge that couple charge neutrality with controlled hydration and dynamic crosslinking to balance conductivity and mechanics. Key gaps include brittleness, ion pairing with multivalent salts, and scale-up. Opportunities include soft segment copolymerization, ionic liquid and DES plasticization, side-chain engineering, and operando studies to guide translation. Full article

Polyampholyte hydrogels are promising for load-bearing biomedical applications, but the link between composition and compression behavior remains unclear. In this study, we investigate how initial monomer concentration and a neutral comonomer influence swelling and mechanical properties in AMPS–APTAC networks. Terpolymeric AMPS–APTAC–DMAAm hydrogels were prepared with monomer concentrations from 1 to 2 M, MBAAm levels from 1 to 5 mol%, and DMAAm fractions from 0 to 0.16. Swelling was measured in water. Unconfined compression tests at 3 mm·min⁻¹ provided stress–strain curves, Young’s modulus (E), fracture stress (σ_f), fracture strain (ε_f), and toughness (W) up to 99% strain. Increasing the monomer concentration produced denser networks, lower swelling, and higher stiffness. For C2M1, E reached 35.4 kPa, σ_f reached 0.8 MPa, ε_f was 82%, and W was 65.6 kJ·m⁻³. Adding DMAAm strengthened the gels through reversible associative interactions. At z = 0.06, σ_f increased to 4.28 MPa and W to 196.0 kJ·m⁻³. At z = 0.16, E increased to 103.0 kPa, while σ_f was 2.34 MPa and W was 191.6 kJ·m⁻³. Swelling decreased when monomer or crosslinker content increased. These results show that monomer concentration and DMAAm-mediated associations act as separate design variables that can be tuned to optimize stiffness, strength, and toughness in AMPS–APTAC polyampholyte hydrogels. Full article

Excessive reservoir water poses significant challenges in the oil and gas industry by diminishing hydrocarbon recovery efficiency and generating environmental and economic complications. Conventional polymer flooding techniques, although beneficial, often prove inadequate under conditions of elevated temperature and salinity, highlighting the need for more resilient materials. In this research, two types of acrylamide-based preformed particle gels (PPGs) were synthesized, as follows: polyelectrolyte and polyampholyte. These PPGs were engineered to improve plugging efficiency and endure extreme reservoir environments. The polyelectrolyte gels were synthesized using acrylamide (AAm) and sodium acrylate (SA), while the polyampholyte gels incorporated AAm, AMPS, and APTAC, with crosslinking achieved through MBAA. The swelling properties, modulated by temperature, salinity, and pH, were evaluated using the Ritger–Peppas and Yavari–Azizian models. The mechanical characteristics and surface morphology of the gels were analyzed using SEM and BET techniques. In sand pack experiments designed to mimic high-permeability reservoirs, the inclusion of 0.5 wt.% of fine PPGs substantially reduced water permeability, outperforming traditional hydrogels. Notably, the polyampholyte PPGs demonstrated superior resilience and efficacy in plugging. However, the experiments were limited by the low test temperature (25 °C) and brine salinity (26.6 g/L). Future investigations will aim to apply these PPGs in high-temperature, fractured carbonate reservoirs. Full article

Preformed particle gels (PPGs) based on acrylamide (AAm), (3-acrylamidopropyl) trimethylammonium chloride (APTAC), and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS) were synthesized via conventional free radical copolymerization. The resultant PPGs of various compositions were characterized using FTIR spectroscopy, TG and DT analysis, and mechanical testing. The swelling behavior of PPGs depending on ionic strength, temperature, degree of crosslinking, and pH was also studied. The obtained results show that the swelling mechanism of PPGs is mainly due to the diffusion of the solvent. The mechanical properties of PPGs were improved by creating a composite polymer network by adding the clay mineral (bentonite) to the reaction mixture of monomers, which also makes it possible to control the Young’s modulus and the swelling degree of the samples. Full article

Polyampholyte hydrogels exhibit great antibacterial and antifouling properties, which make them attractive for biomedical applications, such as drug delivery, wound healing, and tissue engineering. They also have potential applications in food safety, wastewater treatment, and desalination. Since they are based on ionic interactions, polyampholytes are known to require lower amounts of chemical cross-linkers as compared with traditional gels. However, the effects of both chemical and physical interactions on the material’s performance are yet to be fully understood and were examined in the present work. Here, four series of equimolar polyampholyte hydrogels were synthesized with anionic (acrylamidomethylpropane sulfonic acid sodium salt) and cationic monomers (acrylamidopropyl-trimethylammonium chloride) along with a cross-linker (N,N′-methylenebisacrylamide). The mechanical and rheological properties of the gels were characterized following changes to the initial monomer concentration and crosslinker ratios, which led to gels with different toughness, stretchability, and compressibility. The direct correlation of the cross-linking degree with the initial monomer concentration showed that the chemical crosslinker could be further reduced at a high monomer concentration of 30% by weight, which creates an inter-chain network at a minimal crosslinker concentration of 0.25%. Lastly, N′N-dimethylacrylamide was added, which resulted in an increase in the number of H-bonds in the structure, noticeably raising material performance. Full article

We report the rheological behavior of aqueous solutions of a graft copolymer polyampholyte, constituted of polyacrylic acid (PAA) backbone grafted by Poly(L-lysine) (PAA-b-PLL). The graft copolymer self-assembles in aqueous media, forming a three-dimensional (3D) network through polyelectrolyte complexation of the oppositely charged PAA and PLL segments. Rheological investigations showed that the hydrogel exhibits interesting properties, namely, relatively low critical gel concentration, elastic response with slow dynamics, remarkable extended critical strain to flow, shear responsiveness, injectability, 3D printability and self-healing. Due to the weak nature of the involved polyelectrolyte segments, the hydrogel properties display pH-dependency, and they are affected by the presence of salt. Especially upon varying pH, the PLL secondary structure changes from random coil to α-helix, affecting the crosslinking structural mode and, in turn, the overall network structure as reflected in the rheological properties. Thanks to the biocompatibility of the copolymer constituents and the biodegradability of PLL, the designed gelator seems to exhibit potential for bioapplications. Full article

Polyampholyte (PA) hydrogels are randomly copolymerized from anionic and cationic monomers, showing good mechanical properties owing to the existence of numerous ionic bonds in the networks. However, relatively tough PA gels can be synthesized successfully only at high monomer concentrations (C_M), where relatively strong chain entanglements exist to stabilize the primary supramolecular networks. This study aims to toughen weak PA gels with relatively weak primary topological entanglements (at relatively low C_M) via a secondary equilibrium approach. According to this approach, an as-prepared PA gel is first dialyzed in a FeCl₃ solution to reach a swelling equilibrium and then dialyzed in sufficient deionized water to remove excess free ions to achieve a new equilibrium, resulting in the modified PA gels. It is proved that the modified PA gels are eventually constructed by both ionic and metal coordination bonds, which could synergistically enhance the chain interactions and enable the network toughening. Systematic studies indicate that both C_M and FeCl₃ concentration ($C_{{\mathrm{FeCl}}_3}$) influence the enhancement effectiveness of the modified PA gels, although all the gels could be dramatically enhanced. The mechanical properties of the modified PA gel could be optimized at C_M = 2.0 M and $C_{{\mathrm{FeCl}}_3}$ = 0.3 M, where the Young’s modulus, tensile fracture strength, and work of tension are improved by 1800%, 600%, and 820%, respectively, comparing to these of the original PA gel. By selecting a different PA gel system and diverse metal ions (i.e., Al³⁺, Mg²⁺, Ca²⁺), we further prove that the proposed approach is generally appliable. A theoretical model is used to understand the toughening mechanism. This work well extends the simple yet general approach for the toughening of weak PA gels with relatively weak chain entanglements. Full article

Hydrogels with high mechanical strength, good crack resistance, and good adhesion are highly desirable in various areas, such as soft electronics and wound dressing. Yet, these properties are usually mutually exclusive, so achieving such hydrogels is difficult. Herein, we fabricate a series of strong, tough, and adhesive composite hydrogels from polyampholyte (PA) gel reinforced by nonwoven cellulose-based fiber fabric (CF) via a simple composite strategy. In this strategy, CF could form a good interface with the relatively tough PA gel matrix, providing high load-bearing capability and good crack resistance for the composite gels. The relatively soft, sticky PA gel matrix could also provide a large effective contact area to achieve good adhesion. The effect of CF content on the mechanical and adhesion properties of composite gels is systematically studied. The optimized composite gel possesses 35.2 MPa of Young’s modulus, 4.3 MPa of tensile strength, 8.1 kJ m⁻² of tearing energy, 943 kPa of self-adhesive strength, and 1.4 kJ m⁻² of self-adhesive energy, which is 22.1, 2.3, 1.8, 6.0, and 4.2 times those of the gel matrix, respectively. The samples could also form good adhesion to diverse substrates. This work opens a simple route for fabricating strong, tough, and adhesive hydrogels. Full article

With increasing global energy consumption, oil/gas drilling has gradually expanded from conventional shallow reservoirs to deep and ultra-deep reservoirs. However, the harsh geological features including high temperature and high salinity in ultra-deep reservoirs have become a critical challenge faced by water-based drilling fluids (WDFs), which seriously deteriorate the rheology and fluid loss properties, causing drilling accidents, such as wellbore instability and formation collapse. In this study, a novel temperature- and salt-resistant micro-crosslinked polyampholyte gel was synthesized using N,N-dimethylacrylamide, diallyldimethyl ammonium chloride, 2-acrylamido-2-methylpropanesulfonic acid, maleic anhydride and chemical crosslinking agent triallylamine through free radical copolymerization. Due to the synergistic effect of covalent micro-crosslinking and the reverse polyelectrolyte effect of amphoteric polymers, the copolymer-based drilling fluids exhibit outstanding rheological and filtration properties even after aging at high temperatures (up to 200 °C) and high salinity (saturated salt) environments. In addition, the zeta potential and particle size distribution of copolymer-based drilling fluids further confirmed that the copolymer can greatly improve the stability of the base fluid suspension, which is important for reducing the fluid-loss volume of WDFs. Therefore, this work will point out a new direction for the development of temperature- and salt-resistant drilling fluid treatment agents. Full article

pH-sensitive polyampholyte microgels of poly(acrylic acid-co-vinylamine) (P(AA-co-VAm)) were developed as an injectable hydrogel for controlled drug release. The microgels of P(AA-co-VAm) were prepared via inverse suspension polymerization of acrylic acid and N-vinylformamide followed by hydrolysis of poly(N-vinylformamide) (PNVF) chains of the resultant microgels under basic condition. The pH-sensitivity of the P(AA-co-VAm) microgels in zeta potential and swelling ratio were investigated using a zeta potential analyzer and optical microscope. The results showed that both the zeta potential and the swelling ratio of the microgels were highly affected by the solution pH. By changing the pH of P(AA-co-VAm) microgel dispersion, the interparticle interaction and the swelling ratio of the microgels could be well adjusted and a colloidal hydrogel could be fabricated at moderate pH, showing a pH-triggered reversible fluid-gel transition. Using the polyampholyte P(AA-co-VAm) microgels as an injectable hydrogel drug release system, a sustained drug release could be achieved, indicating the great potentials of the pH-sensitive P(AA-co-VAm) microgels for controlled drug delivery. Full article

To study the adsorption of polyampholyte on bentonite (Bent), a block polyampholyte, PAMPS-b-PMAPTAC, comprised of 2-Acrylamido-2-Methylpropane Sulfonic Acid (AMPS) units and Methacrylamido Propyl Trimethyl Ammonium Chloride (MAPTAC) units, was synthesized using reversible addition-fragmentation chain transfer polymerization (RAFT) method. The block polyampholyte samples were characterized by FTIR, ¹H NMR and Gel Permeation Chromatography (GPC). The microstructure of block polyampholyte and random polyampholyte in deionized water indicated that uneven distribution of charged groups increased the entanglement of polymer chains. Addition of salt weakened the electrostatic interactions among charged groups, and, therefore, increased the zeta potential of polyampholyte in aqueous solutions. The adsorptive behaviors of PAMPS-b-PMAPTAC on Bent were studied using elemental analysis, and the effects of external factors were considered. The adsorption equilibrium of polymers on Bent was reached after 12 h. Increased temperature and increased salinity exerted a positive and negative effect on the adsorption of polyampholyte, respectively. The molecular weight played as the decisive factor for the adsorption of polyampholyte in the absence of NaCl, while the content of cationic groups acted as the main factor in the presence of NaCl. Block polyampholyte exhibited higher adsorption than random polyampholyte in the absence of salt. XRD results also indicated that block polyampholyte had a better intercalation effect than random polyampholyte. Full article

Smart hydrogels are promising materials for actuators and sensors, as they can respond to small changes in their environment with a large property change. Hydrogels can respond to a variety of stimuli, for example temperature, pH, metal ions, etc. In this article, the synthesis and characterization of polyampholyte hydrogels based on open chain ligands showing pH and metal ion sensitivity are described. Copolymer and terpolymer gels using different mixtures of monomers i.e., N-[2-(dimethylaminoethyl)acrylamide] (DMAEAAm), N,N-dimethylacrylamide (DMAAm), acrylic acid (AA) and 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS), have been synthesized. The effect of copolymer composition, i.e., the ratio and amount of ionic monomers and the degree of crosslinking on the swelling characteristics, was evaluated as a function of pH. On this basis, metal ion sensitivity measurements were performed at selected pH values. The metal ion sensitivity was measured by varying the concentration of Cu²⁺, Zn²⁺ and Ag⁺ ions under acidic pH conditions. Full article