Kendra A. Erk

Strain Stiffening in Synthetic and Biopolymer Networks

Strain-stiffening behavior common to biopolymer networks is difficult to reproduce in synthetic networks. Physically associating synthetic polymer networks can be an exception to this rule and can demonstrate strain-stiffening behavior at relatively low values of strain. Here, the stiffening behavior of model elastic networks of physically associating triblock copolymers is characterized by shear rheometry. Experiments demonstrate a clear correlation between network structure and strain-stiffening behavior. Stiffening is accurately captured by a constitutive model with a single fitting parameter related to the midblock length. The same model is also effective for describing the stiffening of actin, collagen, and other biopolymer networks. Our synthetic polymer networks could be useful model systems for biological materials due to (1) the observed similarity in strain-stiffening behavior, which can be quantified and related to network structure, and (2) the tunable structure of the physically associating network, which can be manipulated to yield a desired response.

Extreme strain localization and sliding friction in physically associating polymer gels

Model physically associating gels deformed in shear over a wide range of reduced rates displayed evidence of strain localization. The nonlinear stress responses and inhomogeneous velocity profiles observed during shear rheometry coupled with particle tracking velocimetry were associated with the occurrence of rate-dependent banding and fracture-like responses in the gel. Scaling law analysis from traditional sliding friction studies suggests that, at the molecular level, deformation is confined to a shear zone with thickness comparable to the mesh size of the gel, the smallest structurally relevant length scale in the gel.

Shear and dilational interfacial rheology of surfactant-stabilized droplets.

A new measurement method is suggested that is capable of probing the shear and dilational interfacial rheological responses of small droplets, those of size comparable to real emulsion applications. Freely suspended aqueous droplets containing surfactant and non-surface-active tracer particles are transported through a rectangular microchannel by the plane Poiseuille flow of the continuous oil phase. Optical microscopy and high-speed imaging record the shape and internal circulation dynamics of the droplets. Measured circulation velocities are coupled with theoretical descriptions of the droplet dynamics in order to determine the viscous (Boussinesq) and elastic (Marangoni) interfacial effects. A new Marangoni-induced stagnation point is identified theoretically and observed experimentally. Particle velocimetry at only two points (including gradients) in the droplet is sufficient to determine the amplitudes of the dilational and shear responses. We investigate the sensitivity for measuring interfacial properties and compare results from droplets stabilized by a small-molecule surfactant (butanol) and those stabilized by relatively large block copolymer molecules. Future increased availability of shear and dilational interfacial rheological properties is anticipated to lead to improved rules of thumb for emulsion preparation, stabilization, and general practice.

Lignopolymers as viscosity-reducing additives in magnesium oxide suspensions.

Lignopolymers are a new class of polymer additives with the capability to be used as dispersants in cementitious pastes. Made with kraft lignin cores and grafted polymer side-chains, the custom-synthesized lignopolymers were examined in terms of the molecular architecture for viscosity reducing potential in inert model suspensions. Lignin-poly(acrylic acid) (LPAA) and lignin-polyacrylamide (LPAm) have been found to vary the rheology of magnesium oxide (MgO) suspensions based on differences in chain architecture and particle-polymer interactions. A commercial comb-polymer polycarboxylate ester was compared to LPAA and LPAm at 2.7 mg/mL, a typical dosage for cement admixtures, as well as 0.25mg/mL. It was found that LPAm was a more effective viscosity reducer than both LPAA and the commercial additive at low concentrations, which was attributed to greater adsorption on the MgO particle surface and increased steric dispersion from PAm side-chain extension. The influence of chain adsorption and grafted side-chain molecular weight on rheology was also tested.

Improved Concrete Materials with Hydrogel-Based Internal Curing Agents

This research article will describe the design and use of polyelectrolyte hydrogel particles as internal curing agents in concrete and present new results on relevant hydrogel-ion interactions. When incorporated into concrete, hydrogel particles release their stored water to fuel the curing reaction, resulting in reduced volumetric shrinkage and cracking and thus increasing concrete service life. The hydrogel’s swelling performance and mechanical properties are strongly sensitive to multivalent cations that are naturally present in concrete mixtures, including calcium and aluminum. Model poly(acrylic acid(AA)-acrylamide(AM))-based hydrogel particles with different chemical compositions (AA:AM monomer ratio) were synthesized and immersed in sodium, calcium, and aluminum salt solutions. The presence of multivalent cations resulted in decreased swelling capacity and altered swelling kinetics to the point where some hydrogel compositions displayed rapid deswelling behavior and the formation of a mechanically stiff shell. Interestingly, when incorporated into mortar, hydrogel particles reduced mixture shrinkage while encouraging the formation of specific inorganic phases (calcium hydroxide and calcium silicate hydrate) within the void space previously occupied by the swollen particle.

Controllable internal mixing in coalescing droplets induced by the solutal Marangoni convection of surfactants with distinct headgroup architectures

Through several complementary experiments, an investigation of the bulk and interfacial flows that emerged during the coalescence of two water-in-oil droplets with asymmetric compositional properties was performed. By adding surfactant to one of the coalescing droplets and leaving the other surfactant-free, a strong interfacial tension gradient (i.e., solutal Marangoni) driving energy between the merging droplets generated pronounced internal mixing. The contributions of two distinct types of surfactant, anionic ammonium lauryl sulfate (ALS) and cationic cetyltrimethylammonium bromide (CTAB) on the rate of coalescence bridge expansion and on the generation of opposing flows during coalescence were investigated. All coalescence experiments supported the power law relation between the radius of the expanding connective liquid bridge and time, rb ∝ t1/2. However, the presence of surfactant decreased the magnitude of the prefactor in this relationship due to induced interfacial solutal Marangoni convection. Experiments showed that packing efficiency, diffusivity, and bulk concentration of the selected surfactant are vital in solutal Marangoni convection and thus the degree and timescale of internal mixing between merging droplets, which has yet to be adequately discussed within the literature. Denser interfacial packing efficiency and lower diffusivity of CTAB produced stronger opposing bulk and interfacial flow as well as greater bulk mixing. A discussion of how optimized surfactant selection and solutal Marangoni convection can be used for passively inducing convective mixing between coalescing drops in microfluidic channels when viscosity modulation is not feasible is provided.

Synthesis and Characterization of Superabsorbent Polymer Hydrogels Used as Internal Curing Agents: Impact of Particle Shape on Mortar Compressive Strength

Superabsorbent polymer hydrogels have proven to be effective internal curing agents for high-performance concrete because of their ability to absorb and release large amounts of water during hydration and thus mitigate autogenous shrinkage. In this study, the impact of hydrogel particle shape on the microstructure and compressive strength of internally cured mortar was experimentally determined. Inverse suspension polymerization was used to synthesize spherical poly(sodium-acrylate acrylamide) hydrogel particles, while solution polymerization was used to create similarly sized angular particles with identical chemical composition. The hydrogels were characterized with swelling tests in water and cement pore solution. Particle shape did not impact the swelling behavior, and micrographs confirmed that the particles maintained their shape during mixing and placement. Despite the introduction of spherical- and angular-shaped voids from the swollen hydrogel particles, there were no significant differences observed between the compressive strengths of the control mortar and the mortars containing either the spherical or angular hydrogel particles.