The ability to sense applied damage and correlate it with a measurable signal is extremely desirable in any material application to prevent catastrophic failure and the possible loss of use of the material or human injury. Mechanochemistry, in which mechanical forces induce chemical changes, can allow for targeted damage detection by way of embedded mechanophore units, with certain mechanophore chemistries emitting a fluorescent signal in response an applied force. In this work, we successfully employed microparticles of the mechanophore dimeric 9-anthracene carboxylic acid (Di-AC) in a thermoset polyurethane matrix to study their application as universal stress-sensing fillers in network polymer matrix composites. Under a compressive force, there is bond breakage in the mechanically weak cyclooctane photodimers of Di-AC, such that there is reversion to the fluorescent anthracene-type monomers. This fluorescent emission was then correlated to the applied strain, and the precursors to damage were detected with a noticeable fluorescent signal change at an applied strain of only 2%. This early damage detection was additionally possible at very low particle loadings of 2.5 and 5 wt%, with the 5 wt% loading showing enhanced material properties compared to the 2.5 wt%, due to particle reinforcement in the composite. Overall, the synthesis of Di-AC as a stress-sensitive particle filler allows for facile addition of advanced functionality to these ubiquitous thermoset composites.

Iodide-based ionic liquids have been widely employed as sources of iodide in electrolytes for applications utilizing the triiodide/iodide redox couple. While adding a low-viscosity solvent such as water to ionic liquids can greatly enhance their usefulness, mixtures of highly viscous iodide-containing ILs with water have never been studied. Thus, this paper investigates, for the first time, mixtures of water and the ionic liquid 1-butyl-3-methylimidazolium iodide ([BMIM][I]) through a combined experimental and molecular dynamics study. The density, melting point, viscosity and conductivity of these mixtures were measured experimentally. The composition region below 50% water by mole was found to be dramatically different from the region above 50% water, with trends in density and melting point differing before and after that point. Water was found to have a profound effect on viscosity and conductivity of the IL, and the effect of hydrogen bonding was discussed. Molecular dynamics simulations representing the same mixture compositions were performed. Molecular ordering was observed, as were changes in this ordering corresponding to water content. Molecular ordering was related to the experimentally measured mixture properties, providing a possible explanation for the two distinct composition regions identified by experiment.

Poly(ionic liquid)s (PILs) with an intrinsically conducting pyrrole polymer (ICP) backbone were synthesized and utilized as novel dispersants of carbon nanotubes (CNTs) in various polar and nonpolar solvents. This is due to their highly tunable nature, in which the anions can be easily exchanged to form PILs of varying polarity but with the same polycation. These CNT dispersions were exceedingly stable over many months, and with the addition of hexane, Pickering emulsions with the PIL-stabilized CNTs at the droplet interfaces were formed. Depending on the hydrophobicity of the PIL, hexane-in-water and hexane-in-acetonitrile emulsions were formed, the latter marking the first non-aqueous stabilized-CNT emulsions and corresponding CNT-in-acetonitrile dispersion, further advancing the processability of CNTs. The PIL-stabilized CNT Pickering emulsion droplets generated hollow conductive particles by subsequent drying of the emulsions. With the emulsion templating, the hollow shells can be used as a payload carrier, depending on the solubility of the payload in the droplet phase of the emulsion. This was demonstrated with silicon nanoparticles, which have limited solubility in aqueous environments, but great scientific interest due to their potential electrochemical applications. Overall, this work explored a new class of efficient PIL-ICP hybrid stabilizers with tunable hydrophobicity, offering extended stability of carbon nanotube dispersions with novel applications in hollow particle formation via Pickering emulsion templating and in placing payloads into the shells.

The problem of catastrophic damage purveys in any material application, and minimizing its occurrence is paramount for general health and safety. We have successfully synthesized, characterized, and applied dimeric 9-anthracene carboxylic acid (Di-AC)-based mechanophores particles to form stress sensing epoxy matrix composites. As Di-AC had never been previously applied as a mechanophore and thermosets are rarely studied in mechanochemistry, this created an alternative avenue for study in the field. Under an applied stress, the cyclooctane-rings in the Di-AC particles reverted back to their fluorescent anthracene form, which linearly enhanced the overall fluorescence of the composite in response to the applied strain. The fluorescent signal further allowed for stress sensing in the elastic region of the stress\u2014strain curve, which is considered to be a form of damage precursor detection. Overall, the incorporation of Di-AC to the epoxy matrix added much desired stress sensing and damage precursor detection capabilities with good retention of the material properties.

The problem of catastrophic damage purveys in any material application, and minimizing its occurrence is paramount for general health and safety. Thus, novel damage detection schemes are required that can sense the precursors to damage. Mechanochemistry is the area of research that involves the use of mechanical force to induce a chemical change, with recent study focusing on directing the mechanical force to embedded mechanophore units for a targeted chemical response. Mechanophores are molecular units that provide a measureable signal in response to an applied force, often in the form of a visible color change or fluorescent emission, and their application to thermoset network polymers has been limited. Following preliminary work on polymer blends of cyclobutane-based mechanophores and epoxy, dimeric 9-anthracene carboxylic acid (Di-AC)-based mechanophore particles were synthesized and employed to form stress sensitive particle reinforced epoxy matrix composites.

Under an applied stress, the cyclooctane-rings in the Di-AC particles revert back to their fluorescent anthracene form, which linearly enhances the overall fluorescence of the composite in response to the applied strain. The fluorescent signal further allows for stress sensing in the elastic region of the stress-strain curve, which is considered to be a form of damage precursor detection. This behavior was further analyzed at the molecular scale with corresponding molecular dynamics simulations. Following the successful application of Di-AC to an epoxy matrix, the mechanophore particles were incorporated into a polyurethane matrix to show the universal nature of Di-AC as a stress-sensitive particle filler. Interestingly, in polyurethane Di-AC could successfully detect damage with less applied strain compared to the epoxy system.

While mechanophores of varying chemistries have been covalently incorporated into elastomeric and thermoplastic polymer systems, they have not yet been covalently incorporated a thermoset network polymer. Thus, following the study of mechanophore particles as stress-sensitive fillers, two routes of grafting mechanophore units into an epoxy system to form a self-sensing nanocomposite were explored. These involved the mechanophore precursor and mechanophore, cinnamamide and di-cinnamamide, respectively. With both molecules, the free amine groups can directly bond to epoxy resin to covalently incorporate themselves within the thermoset network to form a self-sensing nanocomposite.