A rapid electrochemical method to recycle carbon fiber composites using methyl radicals.

We introduce an electrochemical approach to recycle carbon fiber (CF) fabrics from amine-epoxy carbon fiber-reinforced polymers (CFRPs). Our novel method utilizes a Kolbe-like mechanism to generate methyl radicals from CH3COOH to cleave C-N bonds within epoxy matrices via hydrogen atom abstraction. Recovered CFs are then remanufactured into CFRPs without resizing.

Mechanism and Catalysis of Oxidative Degradation of Fiber-Reinforced Epoxy Composites.

Carbon fiber-reinforced polymer (CFRP) materials are widely used in aerospace and recreational equipment, but there is no efficient procedure for their end-of-life recycling. Ongoing work in the chemistry and engineering communities emphasizes recovering carbon fibers from such waste streams by dissolving or destroying the polymer binding. By contrast, our goal is to depolymerize amine-cured epoxy CFRP composites catalytically, thus enabling not only isolation of high-value carbon fibers, but simultaneously opening an approach to recovery of small molecule monomers that can be used to regenerate precursors to new composite resin. To do so will require understanding of the molecular mechanism(s) of such degradation sequences. Prior work has shown the utility of hydrogen peroxide as a reagent to affect epoxy matrix decomposition [1]. Herein we describe the chemical transformations involved in that sequence: the reaction proceeds by oxygen atom transfer to the polymer's linking aniline group, forming an N-oxide intermediate. The polymer is then cleaved by an elimination and hydrolysis sequence. We find that elimination is the slower step. Scandium trichloride is an efficient catalyst for this step, reducing reaction time in homogeneous model systems and neat cured matrix blocks. The conditions can be applied to composed composite materials, from which pristine carbon fibers can be recovered.

Peptide-Based Bioinspired Approach to Regrowing Multilayered Aprismatic Enamel.

The gradual discovery of functional domains in native enamel matrix proteins has enabled the design of smart bioinspired peptides for tooth enamel mimetics and repair. In this study, we expanded upon the concept of biomineralization to design smaller amelogenin-inspired peptides with conserved functional domains for clinical translation. The synthetic peptides displayed a characteristic nanostructured scaffold reminiscent of 'nanospheres' seen in the enamel matrix and effectively controlled apatite nucleation in vitro resulting in the formation of smaller crystallites. Following application of the peptides to sectioned human molar teeth, a robust, oriented, synthetic aprismatic enamel was observed after 7 days of incubation in situ. There was a two-fold increase in the hardness and modulus of the regrown enamel-like apatite layers and an increase in the attachment of the tooth-regrown layer interface compared to control samples. Repeated peptide applications generated multiple enamel-like hydroxyapatite (HAP) layers of limited thickness produced by epitaxial growth in which c-axis oriented nanorods evolved on the surface of native enamel. We conclude that peptide analogues with active domains can effectively regulate the orientation of regenerated HAP layers to influence functional response. Moreover, this enamel biofabrication approach demonstrates the peptide-mediated growth of multiple microscale HAP arrays of organized microarchitecture with potential for enamel repair.

Carbon nanotube/paraffin/montmorillonite composite phase change material for thermal energy storage.

A composite phase change material (PCM) comprised of organic montmorillonite (OMMT)/paraffin/grafted multi-walled nanotube (MWNT) is synthesized via ultrasonic dispersion and liquid intercalation. The microstructure of the composite PCM has been characterized to determine the phase distribution, and thermal properties (latent heat and thermal conductivity) have been measured by differential scanning calorimetry (DSC) and a thermal constant analyzer. The results show that paraffin molecules are intercalated in the montmorillonite layers and the grafted MWNTs are dispersed in the montmorillonite layers. The latent heat is 47.1 J/g, and the thermal conductivity of the OMMT/paraffin/grafted MWNT composites is 34% higher than that of the OMMT/paraffin composites and 65% higher than that of paraffin.

Assembly of Layered Monetite-Chitosan Nanocomposite and Its Transition to Organized Hydroxyapatite.

Bioinspired synthesis of hierarchically structured calcium phosphate (CaP) material is a highly promising strategy for developing improved bone substitute materials. However, synthesis of CaP materials with outstanding mechanical properties still remains an ongoing challenge. Inspired by the formation of lamellar structure in nacre, we designed an organic matrix composed of chitosan and cis-butenediolic acid (maleic acid, MAc) that could assemble into a layered complex and further guide the mineralization of monetite crystals, resulting in the formation of organized and parallel arrays of monetite platelets with a brick-and-mortar structure. Using the layered monetite-chitosan composite as a precursor, we were able to synthesize hydroxyapatite (HAp) with multiscale hierarchically ordered structure via a topotactic phase transformation process. On the nanoscale, needlelike HAp crystallites assembled into organized bundles that aligned to form highly oriented plates on the microscale. On the large-scale level, these plates with different crystal orientations were stacked together to form a layered structure. The organized structures and composite feature yielded CaP materials with improved mechanical properties close to those of bone. Our study introduces a biomimetic approach that may be practical for the design of advanced, mechanically robust materials for biomedical applications.

Amelogenin Affects Brushite Crystal Morphology and Promotes Its Phase Transformation to Monetite.

Amelogenin protein is involved in organized apatite crystallization during enamel formation. Brushite (CaHPO4·2H2O), one of the precursors of hydroxyapatite mineralization in vitro, has been used for fabrication of biomaterials for hard tissue repair. In order to explore its potential application in biomimetic material synthesis, we studied the influence of the enamel protein amelogenin on brushite morphology and phase transformation to monetite. Our results show that amelogenin can adsorb onto the surface of brushite, leading to the formation of layered morphology on the (010) face. Amelogenin promoted the phase transformation of brushite into monetite (CaHPO4) in the dry state, presumably by interacting with crystalline water layers in brushite unit cells. Changes to the crystal morphology mediated by amelogenin continued even after the phase transformation from brushite to monetite, leading to the formation of organized platelets with an interlocked structure. This effect of amelogenin on brushite morphology and the phase transformation to monetite could provide a new approach to developing biomimetic materials.

Interleukin-21-Producing CD4(+) T Cells Promote Type 2 Immunity to House Dust Mites.

Asthma is a T helper 2 (Th2)-cell-mediated disease; however, recent findings implicate Th17 and innate lymphoid cells also in regulating airway inflammation. Herein, we have demonstrated profound interleukin-21 (IL-21) production after house dust mite (HDM)-driven asthma by using T cell receptor (TCR) transgenic mice reactive to Dermatophagoides pteronyssinus 1 and an IL-21GFP reporter mouse. IL-21-producing cells in the mediastinal lymph node (mLN) bore characteristics of T follicular helper (Tfh) cells, whereas IL-21(+) cells in the lung did not express CXCR5 (a chemokine receptor expressed by Tfh cells) and were distinct from effector Th2 or Th17 cells. Il21r(-/-) mice developed reduced type 2 responses and the IL-21 receptor (IL-21R) enhanced Th2 cell function in a cell-intrinsic manner. Finally, administration of recombinant IL-21 and IL-25 synergistically promoted airway eosinophilia primarily via effects on CD4(+) lymphocytes. This highlights an important Th2-cell-amplifying function of IL-21-producing CD4(+) T cells in allergic airway inflammation.

Amelogenin-chitosan matrix for human enamel regrowth: effects of viscosity and supersaturation degree.

We recently reported an amelogenin-chitosan (CS-AMEL) hydrogel as a promising biomimetic material for future in situ human enamel regrowth. To further optimize the necessary conditions for clinical applicability of CS-AMEL hydrogel, herein we studied the effects of viscosity and supersaturation degree on the size and orientation of synthetic crystals by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). Raising the hydrogel viscosity by increasing chitosan concentration from 1% to 2% (w/v) improved the orientation of the crystals, while a higher supersaturation (σ(HAp) >10.06, [Ca(2+)] >5 mM) resulted in the formation of random crystals with larger sizes and irregular structures. We conclude that optimal conditions to produce organized enamel-like crystals in a CS-AMEL hydrogel are: 2% (w/v) chitosan, 2.5 mM calcium, and 1.5 mM phosphate (degree of supersaturation = 8.23) and 200 µg/ml of amelogenin.

Modified graphene/polyimide nanocomposites: reinforcing and tribological effects.

By taking advantage of design and construction of strong graphene-matrix interfaces, we have prepared modified graphene/polyimide (MG/PI) nanocomposites via a two-stage process consisting of (a) surface modification of graphene and (b) in situ polymerization. The 2 wt % MG/PI nanocomposites exhibited a 20-fold increase in wear resistance and a 12% reduction in friction coefficient, constituting a potential breakthrough for future tribological application. Simultaneously, MG also enhanced thermal stability, electrical conductivity, and mechanical properties, including tensile strength, Young's modulus, storage modulus, and microhardness. Excellent thermal stability and compatibility of interface, strong covalent adhesion interaction and mechanical interlocking at the interface, as well as homogeneous and oriented dispersion of MG were achieved here, contributing to the enhanced properties observed here. The superior wear resistance is ascribed to (a) tribological effect of MG, including suppression effect of MG in the generation of wear debris and protective effect of MG against the friction force, and (b) the increase in mechanical properties. In light of the relatively low cost and the unique properties of graphene, the results of this study highlight a pathway to expand the engineering applications of graphene and solve wear-related mechanical failures of polymer parts.

An amelogenin-chitosan matrix promotes assembly of an enamel-like layer with a dense interface.

Biomimetic reconstruction of tooth enamel is a significant topic of study in materials science and dentistry as a novel approach to the prevention, restoration, and treatment of defective enamel. We have developed a new amelogenin-containing chitosan hydrogel for enamel reconstruction that works through amelogenin supramolecular assembly, stabilizing Ca-P clusters and guiding their arrangement into linear chains. These amelogenin Ca-P composite chains further fuse with enamel crystals and eventually evolve into enamel-like co-aligned crystals, anchored to the natural enamel substrate through a cluster growth process. A dense interface between the newly grown layer and natural enamel was formed and the enamel-like layer improved the hardness and elastic modulus compared with etched enamel. We anticipate that this chitosan hydrogel will provide effective protection against secondary caries because of its pH-responsive and antimicrobial properties. Our studies introduce an amelogenin-containing chitosan hydrogel as a promising biomaterial for enamel repair and demonstrate the potential of applying protein-directed assembly to biomimetic reconstruction of complex biomaterials.

Scaling of membrane-type locally resonant acoustic metamaterial arrays.

Metamaterials have emerged as promising solutions for manipulation of sound waves in a variety of applications. Locally resonant acoustic materials (LRAM) decrease sound transmission by 500% over acoustic mass law predictions at peak transmission loss (TL) frequencies with minimal added mass, making them appealing for weight-critical applications such as aerospace structures. In this study, potential issues associated with scale-up of the structure are addressed. TL of single-celled and multi-celled LRAM was measured using an impedance tube setup with systematic variation in geometric parameters to understand the effects of each parameter on acoustic response. Finite element analysis was performed to predict TL as a function of frequency for structures with varying complexity, including stacked structures and multi-celled arrays. Dynamic response of the array structures under discrete frequency excitation was investigated using laser vibrometry to verify negative dynamic mass behavior.

InGaN/GaN multiple quantum wells grown on nonpolar facets of vertical GaN nanorod arrays.

Uniform GaN nanorod arrays are grown vertically by selective area growth on (left angle bracket 0001 right angle bracket) substrates. The GaN nanorods present six nonpolar {1⁻100} facets, which serve as growth surfaces for InGaN-based light-emitting diode quantum well active regions. Compared to growth on the polar {0001} plane, the piezoelectric fields in the multiple quantum wells (MQWs) can be eliminated when they are grown on nonpolar planes. The capability of growing ordered GaN nanorod arrays with different rod densities is demonstrated. Light emission from InGaN/GaN MQWs grown on the nonpolar facets is investigated by photoluminescence. Local emission from MQWs grown on different regions of GaN nanorods is studied by cathodoluminescence (CL). The core-shell structure of MQWs grown on GaN nanorods is investigated by cross-sectional transmission electron microscopy in both axial and radial directions. The results show that the active MQWs are predominantly grown on nonpolar planes of GaN nanorods, consistent with the observations from CL. The results suggest that GaN nanorod arrays are suitable growth templates for efficient light-emitting diodes.

A thermally re-mendable cross-linked polymeric material.

We have developed a transparent organic polymeric material that can repeatedly mend or "re-mend" itself under mild conditions. The material is a tough solid at room temperature and below with mechanical properties equaling those of commercial epoxy resins. At temperatures above 120 degrees C, approximately 30% (as determined by solid-state nuclear magnetic resonance spectroscopy) of "intermonomer" linkages disconnect but then reconnect upon cooling, This process is fully reversible and can be used to restore a fractured part of the polymer multiple times, and it does not require additional ingredients such as a catalyst, additional monomer, or special surface treatment of the fractured interface.