The mechanical degradation of polymers is typically limited to a single chain scission per triggering chain stretching event, and the loss of stress transfer that results from the scission limits the extent of degradation that can be achieved. Here, we report that the mechanically triggered ring-opening of a [4.2.0]bicyclooctene (BCOE) mechanophore sets up a delayed, force-free cascade lactonization that results in chain scission. Delayed chain scission allows many eventual scission events to be initiated within a single polymer chain. Ultrasonication of a 120 kDa BCOE copolymer mechanically remodels the polymer backbone, and subsequent lactonization slowly (~days) degrades the molecular weight to 4.4 kDa, > 10× smaller than control polymers in which lactonization is blocked. The force-coupled kinetics of ring-opening are probed by single molecule force spectroscopy, and mechanical degradation in the bulk is demonstrated. Delayed scission offers a strategy to enhanced mechanical degradation and programmed obsolescence in structural polymeric materials.
Molecular force probes that generate optical responses to critical levels of mechanical stress (mechanochromophores) are increasingly attractive tools for identifying molecular sites that are most prone to failure. Here, a coumarin dimer mechanophore whose mechanical strength is comparable to that of the sulfur–sulfur bonds found in vulcanized rubbers is reported. It is further shown that the strain‐induced scission of the coumarin dimer within the matrix of a particle‐reinforced polybutadiene‐based co‐polymer can be detected and quantified by fluorescence spectroscopy, when cylinders of the nanocomposite are subjected to unconstrained uniaxial stress. The extent of the scission suggests that the coumarin dimers are molecular “weak links” within the matrix, and, by analogy, sulfur bridges are likely to be the same in vulcanized rubbers. The mechanophore is embedded in polymer main chains, grafting agent, and cross‐linker positions in a polymer composite in order to generate experimental data to understand how macroscopic mechanical stress is transferred at the molecular scale especially in highly entangled cross‐linked polymer nanocomposite. Finally, the extent of activation is enhanced by approximately an order of magnitude by changing the regiochemistry and stereochemistry of the coumarin dimer and embedding the mechanophore at the heterointerface of the particle‐reinforced elastomer.
more » « less- Award ID(s):
- 1808518
- PAR ID:
- 10452623
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Macromolecular Rapid Communications
- Volume:
- 42
- Issue:
- 1
- ISSN:
- 1022-1336
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Understanding the stress distribution within fiber‐reinforced polymers (FRPs) is critical to extending their operational lifespan. The integration of mechanoresponsive molecular force probes, referred to as mechanophores, presents a potential solution by enabling direct monitoring of stress concentrations. In this study, spiropyran (SP) mechanophores (MPs) are embedded within a polydimethylsiloxane (PDMS) matrix to visualize stress localization during loading within a single fiber‐reinforced framework. The SP mechanophore undergoes a transition from a non‐fluorescent state to an active state (merocyanine) through isomerization in response to mechanical forces. Using a single fiber mounted axially within the matrix, the fundamental failure modes observed in conventional fiber‐reinforced composites are replicated. Samples are strained under uniaxial tensile loading along the fiber direction and the localization of stresses is observed via MP activation. Stresses are concentrated in the matrix near the fiber region that gradually decreases away from the fiber surface. Confocal microscopy is used to visualize mechanophore activation and quantitatively assess fluorescence intensity. Finite element modeling is used to develop a calibration to quantify the stresses based on the observed fluorescence intensity. These outcomes underscore the viability of employing these mechanoresponsive molecules as a potential means to visualize real‐time stress distribution, thereby facilitating the design of high‐performance composites.
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Stress concentrations in polymer matrix composites occur due to non-uniform loadings which develop near the interface between the matrix and reinforcement in a stressed composite. Methods to better understand the evolution of this stress concentration are required for the development of advanced composites. Mechanophores, which are stress responsive molecules, can be embedded into the polymer matrix and used to quantify the local stresses in a loaded composite. In this work, single particle model composites were fabricated by combining functionalized glass particles embedded into a silicone/mechanophore matrix. Confocal microscopy was then used to measure the mechanophore activation
in situ during mechanical loading. The fluorescence intensity was correlated to maximum principal stress values obtained from a finite element analysis (FEA) model of the system utilizing an Ogden hyperelastic model to represent the elastomer. By calibrating stress to fluorescence intensity spatially, quantitative stress measurements can be obtained directly from fluorescent images. To validate this technique, calibrated stress values for a two-particle composite system were compared to a FEA model and good agreement was found. Further experiments were performed on silicone matrix composites containing short cylindrical particles oriented with their major axis parallel or perpendicular to the stretching direction. To demonstrate the versatility of the single particle intensity/stress calibration approach, maximum principal stress values were mapped on the fluorescence images of the cylindrical experiments. This technique has potential to quantify stress concentrations quickly and accurately in new composite designs without the use of FEA models or differential image correlation. -
Over the past 20 years, the field of polymer mechanochemistry has amassed a toolbox of mechanophores that translate mechanical energy into a variety of functional responses ranging from color change to small-molecule release. These productive chemical changes typically occur at the length scale of a few covalent bonds (Å) but require large energy inputs and strains on the micro-to-macro scale in order to achieve even low levels of mechanophore activation. The minimal activation hinders the translation of the available chemical responses into materials and device applications. The mechanophore activation challenge inspires core questions at yet another length scale of chemical control, namely: What are the molecular-scale features of a polymeric material that determine the extent of mechanophore activation? Further, how do we marry advances in the chemistry of polymer networks with the chemistry of mechanophores to create stress-responsive materials that are well suited for an intended application? In this Perspective, we speculate as to the potential match between covalent polymer mechanochemistry and recent advances in polymer network chemistry, specifically, topologically controlled networks and the hierarchical material responses enabled by multi-network architectures and mechanically interlocked polymers. Both fundamental and applied opportunities unique to the union of these two fields are discussed.more » « less
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