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.

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.

Structural reinforcement of microvascular networks using electrostatic layer-by-layer assembly with halloysite nanotubes.

We demonstrate a method for tailoring local mechanical properties near channel surfaces of vascular structural polymers in order to achieve high structural performance in microvascular systems. While synthetic vascularized materials have been created by a variety of manufacturing techniques, unreinforced microchannels act as stress concentrators and lead to the initiation of premature failure. Taking inspiration from biological tissues such as dentin and bone, these mechanical deficiencies can be mitigated by complex hierarchical structural features near to channel surfaces. By employing electrostatic layer-by-layer assembly (ELbL) to deposit films containing halloysite nanotubes onto scaffold surfaces followed by matrix infiltration and scaffold removal, we are able to controllably deposit nanoscale reinforcement onto 200 micron diameter channel surface interiors in microvascular networks. High resolution strain measurements on reinforced networks under load verify that the halloysite reduces strain concentrations and improves mechanical performance.

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.

Core-shell polymeric microcapsules with superior thermal and solvent stability.

A protective polydopamine (PDA) coating is applied to core-shell microcapsule surfaces by the polymerization of dopamine monomers. A neutral aqueous solution and the addition of an oxidant (i.e., ammonium persulfate) are crucial for microcapsule survival and the initiation of PDA polymerization, respectively. The resulting PDA coating is a dense and uniform layer approximately 50 nm thick. The PDA protective coating significantly increases capsule stability at an elevated temperature (180 °C) and in a variety of organic solvents and acidic/basic solutions that otherwise lead to deflation and loss of the core content of uncoated microcapsules.

Autonomic healing of acrylic bone cement.

Self-healing in orthopedic bone cement is demonstrated with a novel thermoplastic solvent-bonding approach. Low toxicity solvent-filled microcapsules, embedded in a commercial acrylic bone cement matrix, enable recovery of up to 80% of the virgin fracture toughness of the cement at room and body temperature conditions without external stimuli or human intervention.

A self-healing biomaterial based on free-radical polymerization.

Self-healing chemistry used for damage repair have not previously been demonstrated for free-radical polymerization pathways. However, this chemistry is important for addition polymers such as poly(methyl methacrylate) used in bone cement and epoxy vinyl ester used in dental resins. Self-healing biomaterials offer the potential for safer and longer lasting implants and restoratives by slowing or arresting crack damage. In the free-radical self-healing system reported here, the three components required for polymerization (free-radical peroxide initiator, tertiary amine activator, and vinyl acrylate monomers) are compartmentalized into two separate microcapsules-one containing the peroxide initiator, and the other containing both monomer and activator. Crack damage ruptures the capsules so that the three components mix and react to form a new polymer that effectively rebonds the crack and restores approximately 75% of the original fracture toughness. Optimal healing is obtained by a systematic evaluation of the effect of monomer, initiator, and activator concentration on healing performance.

Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer.

Biological systems rely on recyclable materials resources such as amino acids, carbohydrates and nucleic acids. When biomaterials are damaged as a result of aging or stress, tissues undergo repair by a depolymerization-repolymerization sequence of remodelling. Integration of this concept into synthetic materials systems may lead to devices with extended lifetimes. Here, we show that a metastable polymer, end-capped poly(o-phthalaldehyde), undergoes mechanically initiated depolymerization to revert the material to monomers. Trapping experiments and steered molecular dynamics simulations are consistent with a heterolytic scission mechanism. The obtained monomer was repolymerized by a chemical initiator, effectively completing a depolymerization-repolymerization cycle. By emulating remodelling of biomaterials, this model system suggests the possibility of smart materials where aging or mechanical damage triggers depolymerization, and orthogonal conditions regenerate the polymer when and where necessary.

Triggered transience of metastable poly(phthalaldehyde) for transient electronics.

Triggerable transient electronics are demonstrated with the use of a metastable poly(phthalaldehyde) polymer substrate and encapsulant. The rate of degradation is controlled by the concentration of the photo-acid generator and UV irradiance. This work expands on the materials that can be used for transient electronics by demonstrating transience in response to a preselected trigger without the need for solution-based degradation.

Chemical treatment of poly(lactic acid) fibers to enhance the rate of thermal depolymerization.

When heated, poly(lactic acid) (PLA) fibers depolymerize in a controlled manner, making them potentially useful as sacrificial fibers for microchannel fabrication. Catalysts that increase PLA depolymerization rates are explored and methods to incorporate them into commercially available PLA fibers by a solvent mixture impregnating technique are tested. In the present study, the most active catalysts are identified that are capable of lowering the depolymerization temperature of modified PLA fibers by ca. 100 °C as compared to unmodified ones. Lower depolymerization temperatures allow PLA fibers to be removed from a fully cured epoxy thermoset resin without causing significant thermal damage to the epoxy. For 500 µm diameter PLA fibers, the optimized treatment involves soaking the fibers for 24 h in a solvent mixture containing 60% trifluoroethanol (TFE) and 40% H(2)O dispersed with 10 wt % tin(II) oxalate and subsequent air-drying of the fibers. PLA fibers treated with this procedure are completely removed when heated to 180 °C in vacuo for 20 h. The time evolution of catalytic depolymerization of PLA fiber is investigated by gel permeation chromatography (GPC). Channels fabricated by vaporization of sacrificial components (VaSC) are subsequently characterized by scanning electron microscopy (SEM) and X-ray microtomography (Micro CT) to show the presence of residual catalysts.

Adhesion promotion via noncovalent interactions in self-healing polymers.

Dimethylnorbornene ester (DNE) is successfully used as a noncovalent adhesion promoter. DNE was confirmed to copolymerize with dicyclopentadiene (DCPD) to yield a copolymer with better adhesion to an EPON 828 epoxy matrix relative to poly(DCPD) alone. The mechanical properties of the copolymer were comparable to that of poly(DCPD) alone. An optimized blend of the monomers was encapsulated using a urea-formaldheyde microencapsulation procedure and the resulting capsules were used for in situ self-healing experiments. Improved healing efficiency was observed for samples containing the DCPD/DNE capsules under conditions in which the monomers were efficiently polymerized.

Robust, double-walled microcapsules for self-healing polymeric materials.

Double-walled polyurethane/poly(urea-formaldehyde) microcapsules (PU/UF) are prepared for use in self-healing materials. This modified encapsulation procedure combines two chemistries to form more robust capsule shell walls in a single operation. Robust capsules are formed by this procedure as long as the aromatic polyisocyanate prepolymer is soluble in the core liquid and the core liquid is compatible with isocyanates. Compared to a standard UF encapsulation, the modified procedure results in capsules with an increase in shell wall thickness from 200 to 675 nm as a function of the amount of PU added to the core liquid. Thermal stability of PU/UF microcapsules prepared with varying amounts of PU is compared to UF microcapsules. Mechanical properties of the PU/UF microcapsules are assessed from single-capsule compression testing.

Self-healing materials with microvascular networks.

Self-healing polymers composed of microencapsulated healing agents exhibit remarkable mechanical performance and regenerative ability, but are limited to autonomic repair of a single damage event in a given location. Self-healing is triggered by crack-induced rupture of the embedded capsules; thus, once a localized region is depleted of healing agent, further repair is precluded. Re-mendable polymers can achieve multiple healing cycles, but require external intervention in the form of heat treatment and applied pressure. Here, we report a self-healing system capable of autonomously repairing repeated damage events. Our bio-inspired coating-substrate design delivers healing agent to cracks in a polymer coating via a three-dimensional microvascular network embedded in the substrate. Crack damage in the epoxy coating is healed repeatedly. This approach opens new avenues for continuous delivery of healing agents for self-repair as well as other active species for additional functionality.

Chaotic mixing in three-dimensional microvascular networks fabricated by direct-write assembly.

The creation of geometrically complex fluidic devices is a subject of broad fundamental and technological interest. Here, we demonstrate the fabrication of three-dimensional (3D) microvascular networks through direct-write assembly of a fugitive organic ink. This approach yields a pervasive network of smooth cylindrical channels (approximately 10-300 microm) with defined connectivity. Square-spiral towers, isolated within this vascular network, promote fluid mixing through chaotic advection. These vertical towers give rise to dramatic improvements in mixing relative to simple straight (1D) and square-wave (2D) channels while significantly reducing the device planar footprint. We envisage that 3D microvascular networks will provide an enabling platform for a wide array of fluidic-based applications.