A facile alternative strategy of upcycling mixed plastic waste into vitrimers.

Chemical depolymerization has been identified as a promising approach towards recycling of plastic waste. However, complete depolymerization may be energy intensive with complications in purification. In this work, we have demonstrated upcycling of mixed plastic waste comprising a mixture of polyester, polyamide, and polyurethane through a reprocessable vitrimer of the depolymerized oligomers. Using poly(ethylene terephthalate) (PET) as a model polymer, we first demonstrated partial controlled depolymerization, using glycerol as a cleaving agent, to obtain branched PET oligomers. Recovered PET (RPET) oligomer was then used as a feedstock to produce a crosslinked yet reprocessable vitrimer (vRPET) despite having a wide molecular weight distribution using a solventless melt processing approach. Crosslinking and dynamic interactions were observed through rheology and dynamic mechanical analysis (DMA). Tensile mechanical studies showed no noticeable decrease in mechanical strength over multiple repeated melt processing cycles. Consequently, we have clearly demonstrated the applicability of the above method to upcycle mixed plastic wastes into vitrimers and reprocessable composites. This work also afforded insights into a potentially viable alternative route for utilization of depolymerized plastic/mixed plastic waste into crosslinked vitrimer resins manifesting excellent mechanical strength, while remaining reprocessable/ recyclable for cyclical lifetime use.

In Situ Formation of 3D Conductive and Cell-Laden Graphene Hydrogel for Electrically Regulating Cellular Behavior.

Electroconductive and injectable hydrogels are attracting increasing attention owing to the needs of electrically induced regulation of cell behavior, tissue engineering of electroactive tissues, and achieving minimum invasiveness during tissue repair. In this study, a novel in situ formed 3D conductive and cell-laden hydrogel is developed, which can be broadly used in bioprinting, tissue engineering, neuroengineering etc. An instantaneous, uniform spatial distribution and encapsulation of cells can be achieved as a result of hydrogen bonding induced hydrogel formation. Particularly, the cell-laden hydrogel can be easily obtained by simply mixing and shaking the polydopamine (PDA) functionalized rGO (rGO-PDA) with polyvinyl alcohol (PVA) solution containing cells. Graphene oxide is reduced and functionalized by dopamine to restore the electrical conductivity, while simultaneously enhancing both hydrophilicity and biocompatibility of reduced graphene oxide. In vitro culture of PC12 cells within the cell-laden hydrogel demonstrates its biocompatibility, noncytotoxicity as well as the ability to support long-term cell growth and proliferation. Enhanced neuronal differentiation is also observed, both with and without electrical stimulation. Overall, this 3D conductive, cell-laden hydrogel holds great promise as potential platform for tissue engineering of electroactive tissues.

Design Rationale for Stimuli-Responsive, Semi-interpenetrating Polymer Network Hydrogels-A Quantitative Approach.

Stimuli-responsive semi-interpenetrating polymer network (semi-IPN) hydrogels form an important class of polymers for their tunable properties via molecular design. They are widely investigated for a diverse range of applications including drug delivery, sensors, actuators, and osmotic agents. However, in-depth studies on some of the critical design principles affecting diffusion/leaching of linear polymer from semi-IPN hydrogels are lacking. Herein, for the first time, by preparing a series of model semi-IPN hydrogels based on thermally responsive poly (N-isopropyl acrylamide) (PNIPAM) network and linear poly(sodium acrylate) (PSA), a systematic and quantitative study concerning linear polymer chain retention and swelling/deswelling kinetics is reported. The study shows that PSA retention is significantly affected not only by PSA molecular weight and concentration, but also by polymerization temperature, which could be linked to homogeneity and internal morphology of the hydrogel. Surprisingly, there is no obvious influence of crosslinking density of PNIPAM network toward PSA retention, while faster swelling and deswelling at higher crosslinking density are observed in terms of swelling rate constant and deswelling activation energy. These findings offer new insights on the factors affecting structural and physicochemical properties of such semi-IPN hydrogels, which should in turn serve as a general guideline for materials design.

Salt Template Assisted BN Scaffold Fabrication toward Highly Thermally Conductive Epoxy Composites.

With the trend of device miniaturization and higher integration, polymer composites with high thermal conductivity are highly desirable for efficient removal of accumulated heat to maintain high performance of electronics. In this work, epoxy composites embedded with three-dimensional hexagonal boron nitride (BN) scaffold were fabricated. The BN-poly(vinylidene difluoride) (PVDF) scaffold was prepared by the salt template method using PVDF as the adhesive, while the corresponding epoxy composite was manufactured with vacuum-assisted impregnation. The epoxy/BN-PVDF composite exhibits high thermal conductivity with low loading of BN. The thermal conductivity of epoxy/BN-PVDF composite achieved 1.227 W/(m K) with 21 wt % BN, contributed by the constructed BN pathway held together by PVDF adhesive. In addition, PVDF could be further converted into carbon by thermal treatment, further enhancing the thermal conductivity of epoxy/BN-C composites through alleviating the phonon scattering at the interfaces, eventually obtaining thermal conductivity of 1.466 W/(m K). This type of epoxy-based composite with high thermal conductivity is promising to be used as thermal management materials in advanced electronic devices.

Unraveling the Mechanistic Origins of Epoxy Degradation in Acids.

Water diffusion into polymers like thermosetting epoxies is well-studied; however, comparably little has been reported thus far on the related but very different mechanism of acid diffusion and the corresponding influence on material degradation. The diffusion of hydrochloric acid into an amine-cured epoxy system was studied in this work using gravimetric analysis and dielectric monitoring concurrently, and the mass uptake behavior was observed to differ significantly compared with water diffusion, faster by an order of magnitude. A unique 3-stage diffusion of acid into epoxy was observed due to the influence of Coulombic interactions between oppositely charged ionic species diffusing at different rates. Material characterization studies have revealed that the dominant degradation mechanism is physical in nature, with the formation of surface cracks driven by the swelling stresses due to the core-shell swelling behavior in highly concentrated hydrochloric acid, leading to an erosion-type degradation phenomenon. The insights gained from understanding acid electrolyte diffusion could serve to design a more effective and efficient process to enable thermoset recycling by facilitating rapid material breakdown or the design of acid-resistant materials for various applications in chemical storage tanks, batteries, and protective coatings in a corrosive environment.

Photo-vibrational spectroscopy of solid and liquid chemicals using laser Doppler vibrometer.

Photoacoustic/photothermal spectroscopy is an established technique for trace detection of chemicals and explosives. However, prior sample preparation is required and the analysis is conducted in a sealed space with a high-sensitivity microphone or a piezo sensor coupled with a lock-in amplifier, limiting the technique to applications in a laboratory environment. Due to the aforementioned requirements, traditionally this technique may not be suitable for defense and security applications where the detection of explosives or hazardous chemicals is required in an open environment at a safe standoff distance. In this study, chemicals in various forms (membrane, powder and liquid) were excited by an intensity-modulated quantum cascade laser (QCL), while a laser Doppler vibrometer (LDV) based on the Mach-Zehnder interferometer was applied to detect the vibration signal resulting from the photocoustic/photothermal effect. The photo-vibrational spectrum obtained by scanning the QCL's wavelength in MIR range, coincides well with the corresponding spectrum obtained using typical FTIR equipment. The experiment demonstrated that the LDV is a capable sensor for applications in photoacoustic/photothermal spectroscopy, with potential to enable the detection of chemicals in open environment at safe standoff distance.