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
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.
more » « less- Award ID(s):
- 2045908
- PAR ID:
- 10483318
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Macromolecular Chemistry and Physics
- Volume:
- 224
- Issue:
- 24
- ISSN:
- 1022-1352
- Subject(s) / Keyword(s):
- fiber-reinforced polymer composites fracture mechanics mechanophores polydimethylsiloxane stress localization
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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. -
In recent decades, more than 100 different mechanophores with a broad range of activation forces have been developed. For various applications of mechanophores in polymer materials, it is crucial to selectively activate the mechanophores with high efficiency, avoiding nonspecific bond scission of the material. In this study, we embedded cyclobutane-based mechanophore cross-linkers (I and II) with varied activation forces (fa) in the first network of the double network hydrogels and quantitively investigated the activation selectivity and efficiency of these mechanophores. Our findings revealed that cross-linker I, with a lower activation force relative to the bonds in the polymer main chain (fa-I/fa-chain = 0.8 nN/3.4 nN), achieved efficient activation with 100% selectivity. Conversely, an increase of the activation force of mechanophore II (fa-II/fa-chain = 2.5 nN/3.4 nN) led to a significant decrease of its activation efficiency, accompanied by a substantial number of nonspecific bond scission events. Furthermore, with the coexistence of two cross-linkers, significantly different activation forces resulted in the almost complete suppression of the higher-force one (i.e., I and III, fa-I/fa-III = 0.8 nN/3.4 nN), while similar activation forces led to simultaneous activations with moderate efficiencies (i.e., I and IV, fa-I/fa-IV = 0.8 nN/1.6 nN). These findings provide insights into the prevention of nonspecific bond rupture during mechanophore activation and enhance our understanding of the damage mechanism within polymer networks when using mechanophores as detectors. Besides, it establishes a principle for combining different mechanophores to design multiple mechanoresponsive functional materials.more » « less
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Abstract Most elastomers undergo strain‐induced crystallization (SIC) under tension; as individual chains are held rigidly in a fixed position by an applied strain, their alignment along the strain field results in a shift from strain‐hardening (SH) to SIC. A similar degree of stretching is associated with the tension necessary to accelerate mechanically coupled, covalent chemical responses of mechanophores in overstretched chains, raising the possibility of an interplay between the macroscopic response of SIC and the molecular response of mechanophore activation. Here, thiol‐yne‐derived stereoelastomers doped covalently with a dipropiolate‐derivatized spiropyran (SP) mechanophore (0.25–0.38 mol%) are reported. The material properties of SP‐containing films are consistent with undoped controls, indicating that the SP is a reporter of the mechanical state of the polymer. Uniaxial tensile tests reveal correlations between mechanochromism and SIC, which are strain‐rate‐dependent. When mechanochromic films are stretched slowly to the point of mechanophore activation, the covalently tethered mechanophore remains trapped in a force‐activated state, even after the applied stress is removed. Mechanophore reversion kinetics correlate with the applied strain rate, resulting in highly tunable decoloration rates. Because these polymers are not covalently crosslinked, they are recyclable by melt‐pressing into new films, increasing their potential range of strain‐sensing, morphology‐sensing, and shape‐memory applications.
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1002/macp.202300298
