Rheo-PIV Investigation of Fracture and Self-Healing in a Triblock Copolymer Gel

Physically associating polymer gels have shown the ability to heal after failure, making them promising candidates for various medical applications or consumer products. However, the processes by which these materials self-heal is not well-understood. This study seeks to explain the self-healing behavior of the triblock copolymer poly(methyl methacrylate)-poly(n-butyl acrylate)-poly(methyl methacrylate), or PMMA-PnBA-PMMA, by probing the material’s post-fracture behavior with rheometry and particle image velocimetry (PIV). The self-healing behavior was studied by deforming each gel in shear until failure multiple times with “recovery” periods in-between. PIV was used to verify the occurrence of each fracture in both time and space. Stress relaxation experiments were also performed on the gels to give greater context to the results of the investigation into fracture recovery. Using these data, it was possible to determine the activation energy required for the network chain dissociation and re-association that transpires during the deformation and self-healing of the gel. Stress relaxation experiments yielded an activation energy of 359 kJ/mole for chain dissociation, while fracture-recovery experiments produced an activation energy of 439 kJ/mole for chain re-association. Building upon these insights could lead to a better understanding of the microscopic mechanisms that govern the behavior of intrinsic self-healing materials so that they can be used to their full potential

Characterization of Superabsorbent Polymers in Aluminum Solutions

Over the past few decades, super absorbent polymers (SAPs) have been the topic of research projects all around the world due to their incredible ability to absorb water. They have applications in everything from disposable diapers to high performance concrete. In concrete, aqueous cations permeate the polymer network, reducing swelling and altering properties. One of these ions, aluminum, alters SAP properties by creating a stiff outer shell and greatly reducing absorbency, but these effects have not been well characterized. One method of characterizing the effects of aluminum on SAP hydrogels was performing gravimetric swelling tests to determine equilibrium water capacity at different aluminum ion concentrations. Compressive strength was also determined for swollen particles using a rheometer to perform compression tests. Results from this testing show that low concentration solutions take several hours to permeate the polymer network and reduce swelling capacity, while high concentration solutions are able to limit swelling immediately. The compressive strength of the gel was increased greatly in polymers containing mostly poly(acrylic acid), while SAPs containing more poly(acrylamide) did not have their strength as greatly influenced by the aluminum ions. These results help elucidate the negative effects that may be caused by multivalent cations in concrete. Further research will include studying the interactions of aluminum ions with polymer strands using polymer brushes on a quartz crystal microbalance. This will hopefully reveal the mechanism and kinetics of salt absorption in polymer networks

Characterization of Suspension Polymerized Polyacrylamide and Poly(sodium acrylate-acrylamide) Copolymer and their Size Influence on the Properties of Concrete

Shrinkage leading to cracking and mechanical instability is a major problem for concrete due to the loss of water during the curing process. However, through the addition of Superabsorbent Polymer (SAP) hydrogels, shrinkage can be prevented, increasing the strength of concrete. Characterization of suspension polymerized polyacrylamide (PAM) poly(sodium acrylate-polyacrylamide) (PANa-PAM) copolymer microsphere sizes, morphology and swelling behavior was conducted before adding them to concrete. Size was determined using microscopy paired with ImageJ analysis. Coulter Counter size characterization was also used to determine the particle size distribution. Swelling behavior was determined using the tea bag method as well as size analysis before and after hydration. After characterization, concrete containing various sizes of SAP microspheres will be tested for shrinkage and mechanical strength. These tests will allow us to discover the optimal size of SAP microspheres in concrete to increase its mechanical properties as well as control shrinkage. We will also investigate if the shape of particles has an impact on the final properties of the concrete. The results of this study will contribute to the growing knowledge of applying SAPs in concrete and will give a better understanding on how the size and shape of SAP hydrogels influence the properties of concrete. Using this knowledge, concrete can be made to perform better resulting in more mechanically sound structures

Assessing the Elastic Moduli of Pavement Marking Tapes using the Tape Drape Test

Temporary pavement marking (TPM) tape adhesion with roadway surfaces is critical for tape performance. The two main TPM performance issues both stem from the adhesive strength. Weak adhesion results in premature detachment and excessive adhesion requires extensive removal processes that often leave ghost markings, both of which can cause dangerous confusion in road construction zones. Tape adhesion is directly related to the elastic modulus (E) role= presentation \u3e(E) of TPM tapes. Thus, accurate characterization of E role= presentation \u3eE before tape installation is essential to fully understand and predict the adhesion performance and ultimately the durability of TPMs. To determine the most appropriate E role= presentation \u3eE characterization technique for three different commercial TPM tape brands, two commonly used techniques—tensile and three-point bend testing—were compared with a less common technique, the Peirce cantilever testing or “Tape Drape Test” (ASTM D1388-18). The Tape Drape Test was the only method that accurately characterized E role= presentation \u3eE of tapes with raised surface features. Measured E role= presentation \u3eE values from tensile and three-point bend testing showed significant variation caused by the structural features of the tapes. The Tape Drape Test, which can be implemented quickly in the field before tape installation with little equipment, effectively characterized E role= presentation \u3eE for all the tapes to inform tape adhesion performances and installation procedures

Behavior of Poly electrolyte Gels in Concentrated Solutions of Highly Soluble Salts

Ionic hydrogels are an abundant class of materials with applications ranging from drug delivery devices to high performance concrete to baby diapers. A more thorough understanding of interactions between poly electrolyte networks and ionic solutes is critical as these materials are further tailored for performance applications in highly targeted ionic environments. In this work, we seek to develop structure-property relationships between polyelectrolyte gels and environments containing high concentrations of multivalent ions. Specifically, this work seeks to elucidate the causes behind differences in hydrogel response to divalent ions of main group metals versus transition metals. PANa-co-PAM hydrogels containing low and high fractions of ionic groups are investigated in solutions of DI water, NaCl, CaCl2, and CuSO4 at concentrations ranging from 5 to 100 mM in order to understand 1) the transient or permanent nature of crosslinks produced in these networks by divalent counter-ions, 2) the role of polymer ionic content in these interactions, and 3) how these interactions scale with salt concentration. Gravimetric swelling and mechanical compression testing are employed to characterize water and salt-swollen hydrogels in order to develop guiding principles to control and manipulate material properties through polymer-counter-ion interactions. The work presented here confirms the formation of permanent crosslinks by transition metal ions, offers explanation for the behavioral discrepancy observed between ionic hydrogels and main group versus transition metal ions, and illustrates how such hydrogel properties scale with counter-ion concentration

Superabsorbent Polymers for Internally Cured Concrete

Two commercial superabsorbent polymer (SAP) formulations were used to internally cure cement pastes, mortars, and concretes with a range of water-to-cement ratios (w/c 0.35–0.52). The following properties were determined as a function of cement chemistry and type, use of chemical admixtures, use of slag, and batching parameters: SAP absorption capacity, fresh mixture workability and consistency, degree of hydration, volumetric stability, cracking tendency, compressive and flexural strength, and pumpability. SAP internal curing agents resulted in cementitious mixtures with improved hydration, accelerated strength gain, greater volumetric stability, and improved cracking resistance while maintaining sufficient workability to be pumped and placed without sacrificing compressive or flexural strength. When using SAP, batching adjustments prioritized the use of water reducing admixture instead of extra water to tune workability. While the benefits of SAP internal curing agents for low w/c mixtures were expected, SAP-containing mixtures with w/c ≥ 0.42 displayed accelerated strength development and decreased cracking tendency

Testing superabsorbent polymer (SAP) sorption properties prior to implementation in concrete: results of a RILEM Round-Robin Test

This article presents the results of a round-robin test performed by 13 international research groups in the framework of the activities of the RILEM Technical Committee 260 RSC "Recommendations for use of superabsorbent polymers in concrete construction''. Two commercially available superabsorbent polymers (SAP) with different chemical compositions and gradings were tested in terms of their kinetics of absorption in different media; demineralized water, cement filtrate solution with a particular cement distributed to every participant and a local cement chosen by the participant. Two absorption test methods were considered; the tea-bag method and the filtration method. The absorption capacity was evaluated as a function of time. The results showed correspondence in behaviour of the SAPs among all participants, but also between the two test methods, even though high scatter was observed at early minutes of testing after immersion. The tea-bag method proved to be more practical in terms of time dependent study, whereby the filtration method showed less variation in the absorption capacity after 24 h. However, absorption followed by intrinsic, ionmediated desorption of a specific SAP sample in the course of time was not detected by the filtration method. This SAP-specific characteristic was only displayed by the tea-bag method. This demonstrates the practical applicability of both test methods, each one having their own strengths and weaknesses at distinct testing times

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