An official website of the United States government
Poly(acrylamide- co -acrylic acid) (P(AAm- co -AA)) hydrogels are highly tunable and pH-responsive materials frequently used in biomedical applications. The swelling behavior and mechanical properties of these gels have been extensively characterized and are thought to be controlled by the protonation state of the acrylic acid (AA) through the regulation of solution pH. However, their tribological properties have been underexplored. Here, we hypothesized that electrostatics and the protonation state of AA would drive the tribological properties of these polyelectrolyte gels. P(AAm- co -AA) hydrogels were prepared with constant acrylamide (AAm) concentration (33 wt%) and varying AA concentration to control the amount of ionizable groups in the gel. The monomer:crosslinker molar ratio (200:1) was kept constant. Hydrogel swelling, stiffness, and friction behavior were studied by systematically varying the acrylic acid (AA) concentration from 0–12 wt% and controlling solution pH (0.35, 7, 13.8) and ionic strength ( I = 0 or 0.25 M). The stiffness and friction coefficient of bulk hydrogels were evaluated using a microtribometer and borosilicate glass probes as countersurfaces. The swelling behavior and elastic modulus of these polyelectrolyte hydrogels were highly sensitive to solution pH and poorly predicted the friction coefficient ( µ ), which decreased with increasing AA concentration. P(AAm- co -AA) hydrogels with the greatest AA concentrations (12 wt%) exhibited superlubricity ( µ = 0.005 ± 0.001) when swollen in unbuffered, deionized water (pH = 7, I = 0 M) and 0.5 M NaOH (pH = 13.8, I = 0.25 M) ( µ = 0.005 ± 0.002). Friction coefficients generally decreased with increasing AA and increasing solution pH. We postulate that tunable lubricity in P(AAm- co -AA) gels arises from changes in the protonation state of acrylic acid and electrostatic interactions between the probe and hydrogel surface.
more »
« less
This content will become publicly available on September 23, 2026
Ionic Control of Microstructure and Lubrication in Charged, Physically Cross‐Linked Hydrogels
Charged, physically cross‐linked hydrogels provide a versatile platform for designing responsive materials with programmable interfacial properties, with applications in drug delivery, biomedical devices, and biosensing. Here, poly(methacrylamide‐co‐methacrylic acid) hydrogels stabilized by a short‐range attractive, long‐range repulsive potential is investigated. By integrating microstructural, mechanical, and tribological characterization across multiple length and time scales, this work uncovers how salt addition alters not only swelling, but also the microstructure and dynamics, near‐surface stiffness and charge, and ultimately, its lubricity. Friction measurements reveal a velocity‐dependent response with distinct mixed, transition, and elastohydrodynamic regimes. Microscopic friction imaging reveals that adhesive interactions are promoted by salt and play a critical role. Unlike neutral hydrogels, where increased water content correlates with reduced friction, salts introduce additional dissipation mechanisms that can dominate over hydration effects, offering enhanced control of functional behavior. These findings provide new insights into the salt‐induced responsive behavior of poly(methacrylamide‐co‐methacrylic acid) hydrogels‐including lubrication mechanisms‐and challenges conventional interpretations of salt effects in polyelectrolyte systems. This knowledge will inform design principles for synthetic hydrogel interfaces and advance understanding of the functional behavior of hydrogel‐like materials such as biological tissues, whose lubricity‐in salinity conditions similar to those studied here‐is essential to their function.
more »
« less
- PAR ID:
- 10654792
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Advanced Functional Materials
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Despite recent advances in polyelectrolyte systems, designing responsive hydrogel interfaces to meet application requirements still proves challenging. Here, semicrystalline colloidal gels composed of poly(methacrylamide‐co‐methacrylic acid) are investigated in water with storage moduli in the MPa range. A combination of SEM, X‐ray scattering, and NMR reveals the evolution of the colloidal microstructure, crystallinity, and hydrogen bonding with varying monomer ratio. The gels with the finest colloidal microstructure exhibit the most dissipative rheological behavior and are selected for the study of their interfacial characteristics and underlying interactions. Microstructure stabilization and dynamics results from short‐range (attractive) hydrogen bonding and hydrophobic forces, and long‐range (repulsive) electrostatic interactions—the “SALR” pair potential. Further, the gel's surface exhibits a submicron colloidal topography that greatly determines (colloidal‐like) friction as a result of the viscoelastic deformation of the colloidal network, while electrostatic near‐surface interactions propagate in lamellar adhesion. The dynamic and reversible nature of the involved interactions introduces a stimulus responsive behavior that enables the electrotunability of adhesion and friction. This study advances the knowledge necessary to design complex hydrogel interfaces that enable spatial and dynamic control of surface properties, which is of relevance for applications in biomedical devices, soft tissue design, soft robotics, and other engineered tribosystems.more » « less
-
Abstract Non‐spherical stimuli‐responsive polymeric particles have shown critical importance in therapeutic delivery. Herein, pH‐responsive poly(methacrylic acid) (PMAA) cubic hydrogel microparticles are synthesized by crosslinking PMAA layers within PMAA/poly(N‐vinylpyrrolidone) hydrogen‐bonded multilayers templated on porous inorganic microparticles. This study investigates the effects of template porosity and surface morphology on the PMAA multilayer hydrogel microcube properties. It is found that the hydrogel structure depends on the template's calcination time and temperature. The pH‐triggered PMAA hydrogel cube swelling depends on the hydrogel's internal architecture, either hollow capsule‐like or non‐hollow continuous hydrogels. The loading efficiency of the doxorubicin (DOX) drug inside the microcubes is analyzed by high‐performance liquid chromatography (HPLC), and shows the dependenceof the drug uptake on the network structure and morphology controlled by the template porosity. Varying the template calcination from low (300 °C) to high (1000 °C) temperature results in a 2.5‐fold greater DOX encapsulation by the hydrogel cubes. The effects of hydrogel surface charge on the DOX loading and release are also studied using zeta‐potential measurements. This work provides insight into the effect of structural composition, network morphology, and pH‐induced swelling of the cubical hydrogels and may advance the development of stimuli‐responsive vehicles for targeted anticancer drug delivery.more » « less
-
Stimuli-responsive hydrogels with self-strengthening properties are promising for the use of autonomous growth and adaptation systems to the surrounding environments by mimicking biological materials. However, conventional stimuli-responsive hydrogels require structural destruction to initiate mechanochemical reactions to grow new polymeric networks and strengthen themselves. Here we report continuous self-strengthening of a nanocomposite hydrogel composed of poly( N -isopropylacrylamide) (PNIPAM) and nanoclay (NC) by using external stimuli such as heat and ionic strength. The internal structures of the NC-PNIPAM hydrogel are rearranged through the swelling–deswelling cycles or immersing in a salt solution, thus its mechanical properties are significantly improved. The effects of concentration of NC in hydrogels, number of swelling–deswelling cycles, and presence of salt in the surrounding environment on the mechanical properties of hydrogels are characterized by nanoindentation and tensile tests. The self-strengthening mechanical performance of the hydrogels is demonstrated by the loading ability. This work may offer promise for applications such as artificial muscles and soft robotics.more » « less
-
Abstract Charged double network (DN) hydrogels are widely studied for their desirable mechanical strength and tunable properties. In this work, the influence of polymer concentration on microstructure and properties of agarose/polyacrylic acid DN hydrogels is studied. Agarose, the first network, is a brittle biopolymer, while polyacrylic acid (PAAc) is a weak polyelectrolyte. The microstructure, visualized in liquid environment, displays an agarose scaffold coated and interconnected by PAAc, deviating from the common assumption of an entangled double network. Importantly, the charging of PAAc in the hydrogel is regulated not only by the pH and weak polyelectrolyte effects, but also by the restricted swelling of the double network, and hence, it is an inherent regulation mechanism of charged hydrogels. The interactions between the hydrogel and the ionic environment induce microstructural changes and charging of the double network, impacting surface properties such as topography, stiffness, and adhesion, which are spatially resolved by liquid‐environment atomic force microscopy. The responsiveness of the DN hydrogels significantly depends on both polymer concentrations and ion concentrations. These findings provide insights into the responsive behavior of double network hydrogels and reveal universal mechanisms for charged hydrogels, which can guide the future development of functional soft materials.more » « less
