Localization of Spiropyran Activation.

Functionalization of planar and curved glass surfaces with spiropyran (SP) molecules and localized UV-induced activation of the mechanophore are demonstrated. Fluorescence spectra of UV-irradiated SP-functionalized surfaces reveal that increases in surface roughness or curvature produce more efficient conversion of the mechanophore to the open merocyanine (MC) form. Further, force-induced activation of the mechanophore is achieved at curved glass-polymer interfaces and not planar interfaces. Minimal fluorescence signal from UV-irradiated SP-functionalized planar glass surfaces precluded mechanical activation testing. Curved glass-polymer interfaces are prepared by SP functionalization of E-glass fibers, which are subsequently embedded in a poly(methyl methacrylate) (PMMA) matrix. Mechanical activation is induced through shear loading by a single fiber microbond testing protocol. In situ detection of SP activation at the interface is monitored by fluorescence spectroscopy. The fluorescence increase during interfacial testing suggests that attachment of the interfacial SP molecule to both fiber surface and polymer matrix is present and able to achieve significant activation of SP at the fiber-polymer matrix interface. Unlike previous studies for bulk polymers, SP activation is detected at relatively low levels of applied shear stress. By linking SP at the glass-polymer interface and transferring load directly to that interface, a more efficient mechanism for eliciting the SP response is achieved.

Rapid Degradation of Poly(lactic acid) with Organometallic Catalysts.

Poly(lactic acid) (PLA) is an effective sacrificial material for the creation of vascular networks in thermoset polymers and composites. The high thermal stability of PLA limits its applications as an embedded sacrificial template in high-temperature-resistant thermoset matrices. Here, we demonstrate faster and more efficient PLA degradation at temperatures lower than previously reported using two organometallic catalysts: tin(II) oxalate (Sn(Oxa)) and tin(II) acetate (Sn(Ac)2). We process Sn(Oxa) by two separate methods to obtain a significant difference in the specific surface area (SSA) of the catalyst particles and compare PLA degradation performance in a thermogravimetric analysis (TGA) instrument. Changing the SSA of Sn(Oxa) by a factor of ∼20 reduces the PLA degradation onset temperature by 37 °C. The total degradation time of PLA films also decreases after blending with Sn(Oxa) having a higher SSA. We also find Sn(Ac)2 lowers the degradation onset of PLA by 53 °C compared to Sn(Oxa) with a similar SSA. In addition, Sn(Ac)2 decreases the time for complete degradation of PLA films by an order of magnitude compared to Sn(Oxa) at 200 °C. Films with a significantly lower Sn(Ac)2 concentration compared to Sn(Oxa) degrade much faster at lower temperatures up to 160 °C. Finally, PLA films with different loadings of Sn(Ac)2 are embedded in an epoxy thermoset matrix and subsequently vascularized at elevated temperatures in a vacuum oven. Microchannel formation is observed at 170 °C using Sn(Ac)2, reducing the temperature required for vaporization of embedded sacrificial polymer compared to Sn(Oxa) catalyst. Sn(Ac)2 can potentially reduce the energy, time, and amount of catalyst required for degrading PLA into volatile products for sacrificial applications.

Enhanced Mixing of Microvascular Self-Healing Reagents Using Segmented Gas-Liquid Flow.

Microvascular self-healing systems have previously been demonstrated to restore large-scale damage and achieve repeated healing of multiple damage events in polymers. However, the healing performance of these systems is often limited because the laminar nature of flow in microchannels  results in poor mixing of two-part self-healing reagents. In this paper, we introduce segmented gas-liquid flow (SGLF) to enhance the mixing of reagents in microvascular self-healing systems. In SGLF, discrete liquid slugs containing self-healing reagents are separated by gas bubbles while flowing through a single microchannel. Recirculating streamlines within the liquid slugs can enhance the mixing of miscible liquids such as healing reagents. We investigate the effect of SGLF on mixing and healing for a two-stage chemistry used to restore large-scale damage in thermoset polymers. Additionally, we employ SGLF to deliver an epoxy-thiol chemistry, enabling the repeated recovery of fracture toughness in glass fiber-reinforced composites. In both systems, the mixing of healing agents delivered by SGLF is enhanced compared to alternative microvascular delivery strategies. For the two-stage chemistry, SGLF increases the maximum damage size that can be healed by 25% compared to laminar single-phase flow. Furthermore, there are concomitant increases in the extent of polymerization and the mechanical properties of the restored material, including a fivefold increase in the peak load sustained during a push-out test. For the epoxy-thiol chemistry, SGLF enables multiple healing cycles with healing efficiency above 100%. On the basis of these results, we envision that SGLF could improve performance for a variety of microvascular self-healing systems with different host materials, damage modes, and healing chemistries.

Core-Shell Microcapsules Containing Flame Retardant Tris(2-chloroethyl phosphate) for Lithium-Ion Battery Applications.

Flame retardant tris(2-chloroethyl phosphate) (TCP) is successfully encapsulated in core-shell poly(urea-formaldehyde) microcapsules by in situ polymerization. The microcapsules are electrochemically stable in lithium-ion (Li-ion) battery electrolytes and thermally stable to ca. 200 °C. Thermal triggering of these microcapsules at higher temperatures ruptures the shell wall, releasing the liquid core (flame retardant), and NMR spectroscopy confirms the presence of the flame retardant in the electrolyte solution. Li-ion pouch cell experiments demonstrate that microencapsulation of TCP and its incorporation into the battery electrolyte provide latent fire retardants that improve battery safety while maintaining inherent battery performance and cycling capability.

Rapid energy-efficient manufacturing of polymers and composites via frontal polymerization.

Thermoset polymers and composite materials are integral to today's aerospace, automotive, marine and energy industries and will be vital to the next generation of lightweight, energy-efficient structures in these enterprises, owing to their excellent specific stiffness and strength, thermal stability and chemical resistance1-5. The manufacture of high-performance thermoset components requires the monomer to be cured at high temperatures (around 180 °C) for several hours, under a combined external pressure and internal vacuum 6 . Curing is generally accomplished using large autoclaves or ovens that scale in size with the component. Hence this traditional curing approach is slow, requires a large amount of energy and involves substantial capital investment6,7. Frontal polymerization is a promising alternative curing strategy, in which a self-propagating exothermic reaction wave transforms liquid monomers to fully cured polymers. We report here the frontal polymerization of a high-performance thermoset polymer that allows the rapid fabrication of parts with microscale features, three-dimensional printed structures and carbon-fibre-reinforced polymer composites. Precise control of the polymerization kinetics at both ambient and elevated temperatures allows stable monomer solutions to transform into fully cured polymers within seconds, reducing energy requirements and cure times by several orders of magnitude compared with conventional oven or autoclave curing approaches. The resulting polymer and composite parts possess similar mechanical properties to those cured conventionally. This curing strategy greatly improves the efficiency of manufacturing of high-performance polymers and composites, and is widely applicable to many industries.

Accelerated Thermal Depolymerization of Cyclic Polyphthalaldehyde with a Polymeric Thermoacid Generator.

Thermally triggerable polymer films that degrade at modest temperatures (≈85 °C) are created from a blend of cyclic polyphthalaldehyde (cPPA) and a polymeric thermoacid generator, poly(vinyl tert-butyl carbonate sulfone) (PVtBCS). PVtBCS depolymerizes when heated, generating acid which initiates the depolymerization of cPPA into volatile byproducts. The mass loss onset for 2 wt% PVtBCS/cPPA is 22 °C lower than the onset for neat cPPA alone in dynamic thermogravimetric analysis experiments. Increased concentrations of PVtBCS increase the rate of depolymerization of cPPA. Raman spectroscopy reveals that the monomer, o-phthalaldehyde, is the main depolymerization product of the acid-catalyzed depolymerization of cPPA. The PVtBCS/cPPA blend is a promising material for the design and manufacture of transient electronic packaging and polymers.

Interfacial Mechanophore Activation Using Laser-Induced Stress Waves.

A new methodology is developed to activate and characterize mechanochemical transformations at a solid interface. Maleimide-anthracene mechanophores covalently anchored at a fused silica-polymer interface are activated using laser-induced stress waves. Spallation-induced mechanophore activation is observed above a threshold activation stress of 149 MPa. The retro [4+2] cycloaddition reaction is confirmed by fluorescence microscopy, XPS, and ToF-SIMS measurements. Control experiments with specimens in which the mechanophore is not covalently attached to the polymer layer exhibit no activation. In contrast to activation in solution or bulk polymers, whereby a proportional increase in mechanophore activity is observed with applied stress, interfacial activation occurs collectively with spallation of the polymer film.

Self-Protecting Epoxy Coatings with Anticorrosion Microcapsules.

The corrosion of steel substrates causes damage that is costly to repair or replace. Current protective coatings predominately rely on environmentally harmful anticorrosive agents and toxic solvents to protect the underlying substrate. The use of lawsone (2-hydroxy-1,4-napthoquinone) together with a water-based epoxy coating provides an environmentally friendly alternative for common protective coatings. Microencapsulated lawsone embedded in an epoxy coating allows the anticorrosive agent to remain dormant until released by damage and delivered directly onto the steel substrate. UV-vis analysis confirms successful encapsulation of lawsone in a polyurethane shell wall and reveals up to 8 wt % lawsone in the capsule cores. Uniform dry film thickness and inflicted damaged are verified with ultrasound and optical microscopy. Visual and electrochemical analysis demonstrates that this self-protective scheme leads to a 70% corrosion inhibition efficiency in a neutral salt water solution.

Cyclic Poly(phthalaldehyde): Thermoforming a Bulk Transient Material.

Cyclic poly(phthalaldehyde) (cPPA) is a metastable and stimuli responsive polymer that undergoes rapid solid state depolymerization and has been utilized as a packaging and encapsulating material for transient applications. However, the early onset thermal depolymerization of cPPA severely hinders the fabrication and processing of plastic parts. Herein, the thermally triggered depolymerization of cPPA was investigated and tailored to enable thermal processing and molding of cPPA at moderate temperatures below the thermal depolymerization temperature. Stabilization of cPPA at elevated temperature was accomplished by removal of the latent Lewis acid catalyst BF3 and by addition of radical inhibitors and a Lewis base. Addition of a plasticizer to the stabilized cPPA enabled the fabrication of a monolithic solid polymer via hot press molding. Importantly, it is shown that the thermally processed cPPA retains its stimuli responsive depolymerization capability and will enable future work in the fabrication of bulk plastic parts that depolymerize and disintegrate on demand.

Time Release of Encapsulated Additives for Enhanced Performance of Lithium-Ion Batteries.

Time release of encapsulated vinylene carbonate (VC) from microcapsules in Li-ion batteries is demonstrated to enhance the rate performance without sacrificing capacity retention. VC-filled microcapsules are successfully prepared by the solvent exchange method that allows VC to diffuse through the microcapsule shell wall at an elevated temperature. The concentration of VC added directly to the electrolyte in a pouch cell (2 wt %) significantly decreases after the first cycle at C/10-rate. In pouch cells that contain 5 wt % VC-filled microcapsules, the concentration of VC increases from 0 to 3 wt % over the first cycle because of the diffusion of microencapsulated VC in the electrolyte. Electrochemical impedance spectroscopy, rate capability, and long-term cycling tests are conducted for pouch cells with VC additives (0, 2, and 5 wt %) and VC microcapsules (5 wt %). Pouch cells with both 5 wt % VC additive and microencapsulated VC show improved capacity retention over 400 cycles at 1 C-rate compared to the cells without VC additive. When VC is added directly, the high initial concentration leads to increased interfacial resistance and decreased rate capability. By contrast, time release of microencapsulated VC by diffusion through microcapsules increases the discharge capacity 2.5 times at 5 C-rate compared to the direct VC addition to the electrolyte.

Low-Ceiling-Temperature Polymer Microcapsules with Hydrophobic Payloads via Rapid Emulsion-Solvent Evaporation.

We report a microencapsulation procedure based on rapid solvent evaporation to prepare microcapsules with hydrophobic core materials and low-ceiling-temperature polymer shell wall of cyclic poly(phthalaldehyde) (cPPA). We use and compare microfluidic and bulk emulsions. In both methods, rapid solvent evaporation following emulsification resulted in kinetically trapped core-shell microcapsules, whereas slow evaporation resulted in acorn morphology. Through the systematic variation of encapsulation parameters, we found that polymer-to-core weight ratios higher than 1 and polymer concentrations higher than 4.5 wt % in the oil phase were required to obtain a core-shell structure. This microencapsulation procedure enabled the fabrication of microcapsules with high core loading, controlled size, morphology, and stability. This procedure is versatile, allowing for the encapsulation of other hydrophobic core materials, i.e., mineral oil and organotin catalyst, or using an alternative low-ceiling-temperature polymer shell wall, poly(vinyl tert-butyl carbonate sulfone).

Encapsulation of grape seed extract in polylactide microcapsules for sustained bioactivity and time-dependent release in dental material applications.

OBJECTIVE: To sustain the bioactivity of proanthocyanidins-rich plant-derived extracts via encapsulation within biodegradable polymer microcapsules. METHODS: Polylactide microcapsules containing grape seed extract (GSE) were manufactured using a combination of double emulsion and solvent evaporation techniques. Microcapsule morphology, size distribution, and cross-section were examined via scanning electron microscopy. UV-vis measurements were carried out to evaluate the core loading and encapsulation efficiency of microcapsules. The bioactivity of extracts was evaluated after extraction from capsules via solvent partitioning one week or one year post-encapsulation process. Fifteen human molars were cut into 7mm×1.7mm×0.5mm thick mid-coronal dentin beams, demineralized, and treated with either encapsulated GSE, pristine GSE, or left untreated. The elastic modulus of dentin specimens was measured based on three-point bending experiments as an indirect assessment of the bioactivity of grape seed extracts. The effects of the encapsulation process and storage time on the bioactivity of extracts were analyzed. RESULTS: Polynuclear microcapsules with average diameter of 1.38µm and core loading of up to 38wt% were successfully manufactured. There were no statistically significant differences in the mean fold increase of elastic modulus values among the samples treated with encapsulated or pristine GSE (p=0.333), or the storage time (one week versus one year storage at room temperature, p=0.967). SIGNIFICANCE: Polynuclear microcapsules containing proanthocyanidins-rich plant-derived extracts were prepared. The bioactivity of extracts was preserved after microencapsulation.

Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life.

Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.

Polymers with autonomous life-cycle control.

The lifetime of man-made materials is controlled largely by the wear and tear of everyday use, environmental stress and unexpected damage, which ultimately lead to failure and disposal. Smart materials that mimic the ability of living systems to autonomously protect, report, heal and even regenerate in response to damage could increase the lifetime, safety and sustainability of many manufactured items. There are several approaches to achieving these functions using polymer-based materials, but making them work in highly variable, real-world situations is proving challenging.

A Robust Damage-Reporting Strategy for Polymeric Materials Enabled by Aggregation-Induced Emission.

Microscopic damage inevitably leads to failure in polymers and composite materials, but it is difficult to detect without the aid of specialized equipment. The ability to enhance the detection of small-scale damage prior to catastrophic material failure is important for improving the safety and reliability of critical engineering components, while simultaneously reducing life cycle costs associated with regular maintenance and inspection. Here, we demonstrate a simple, robust, and sensitive fluorescence-based approach for autonomous detection of damage in polymeric materials and composites enabled by aggregation-induced emission (AIE). This simple, yet powerful system relies on a single active component, and the general mechanism delivers outstanding performance in a wide variety of materials with diverse chemical and mechanical properties.

Regioisomer-Specific Mechanochromism of Naphthopyran in Polymeric Materials.

Transformation of naphthopyran into a colored merocyanine species in polymeric materials is achieved using mechanical force. We demonstrate that the mechanochemical reactivity of naphthopyran is critically dependent on the regiochemistry, with only one particular substitution pattern leading to successful mechanochemical activation. Two alternative regioisomers with different polymer attachment points are demonstrated to be mechanochemically inactive. This trend in reactivity is accurately predicted by DFT calculations, reinforcing predictive capabilities in mechanochemical systems. We rationalize the reactivity differences between naphthopyran regioisomers in terms of the alignment of the target C-O pyran bond with the direction of the applied mechanical force and its effect on mechanochemical transduction along the reaction coordinate.

Malleable and Recyclable Poly(urea-urethane) Thermosets bearing Hindered Urea Bonds.

Poly(urea-urethane) thermosets containing the 1-tert-butylethylurea (TBEU) structure feature a reversible dissociation/association process of their covalent linkages under mild conditions. Unlike conventional thermosets, TBEU-based poly(urea-urethane) thermosets maintain their malleability after curing. Under high temperature (100 °C) and applied pressure (300 kPa), ground TBEU thermoset powder can be remolded to bulk after 20 min.

Autonomous Indication of Mechanical Damage in Polymeric Coatings.

High-resolution in situ autonomous visual indication of mechanical damage is achieved through a microcapsule-based polymeric material system. Upon mechanical damage, ruptured microcapsules release a liquid indicator molecule. A sharp color change from light yellow to bright red is triggered when the liberated indicator 2',7'-dichlorofluorescein reacts with the polymeric coating matrix.

Effect of Mechanical Stress on Spiropyran-Merocyanine Reaction Kinetics in a Thermoplastic Polymer.

Mechanical force alters the potential energy surface of a mechanophore reaction by modifying the activation energy for conversion. The effects of force on the rate constants and activation energies are not well characterized for mechanophores in bulk polymers. In this work, spiropyran-linked polyurethanes are synthesized and the kinetics of the spiropyran-merocyanine transition in the bulk polymer measured under different values of a macroscopic tensile stress. Above a critical threshold stress, the forward rate constant (spiropyran to merocyanine transition) increases, while the reverse rate constant (merocyanine to spiropyran transition) decreases with applied stress. A tensile stress of 50 MPa enhances the forward rate constant by 110% and lowers the forward activation energy by 1.8 kJ/mol compared to the unstressed condition. Also, this same amount of stress reduces the reverse rate constant by 65% and increases the reverse activation energy by 2.5 kJ/mol.