A Highly Elastic and Reversibly Stretchable All-Polymer Supercapacitor.

Multiple stretchability has never been demonstrated as supercapacitors because the hydrogel used cannot fully recover after being heavily deformed. Now, a highly reversibly stretchable all-polymer supercapacitor was fabricated using a developed double network hydrogel (DN hydrogel) as electrolyte and pure polypyrrole (PPy) as electrode. The DN hydrogel provides excellent mechanical properties, which can be stretched up to 500 % many times and then restore almost 100 % of the original length. To fabricate the fully recoverable stretchable supercapacitor, we annealed a free-standing pure conducting polymer film as electrode so that the electrodes induced retardance is minimized. The as-fabricated DN hydrogel/pure conducting polymer supercapacitors can be perfectly recovered from 100 % strain with almost no residual deformation left and the electrochemical performance can be maintained even after 1000 stretches (but not bending).

Fabrication of High Gas Barrier Epoxy Nanocomposites: An Approach Based on Layered Silicate Functionalized by a Compatible and Reactive Modifier of Epoxy-Diamine Adduct.

To solve the drawbacks of poor dispersion and weak interface in gas barrier nanocomposites, a novel epoxy-diamine adduct (DDA) was synthesized by reacting epoxy monomer DGEBA with curing agent D400 to functionalize montmorillonite (MMT), which could provide complete compatibility and reactivity with a DGEBA/D400 epoxy matrix. Thereafter, sodium type montmorillonite (Na-MMT) and organic-MMTs functionalized by DDA and polyether amines were incorporated with epoxy to manufacture nanocomposites. The effects of MMT functionalization on the morphology and gas barrier property of nanocomposites were evaluated. The results showed that DDA was successfully synthesized, terminating with epoxy and amine groups. By simulating the small-angle neutron scattering data with a sandwich structure model, the optimal dispersion/exfoliation of MMT was observed in a DDA-MMT/DGEBA nanocomposite with a mean radius of 751 Å, a layer thickness of 30.8 Å, and only two layers in each tactoid. Moreover, the DDA-MMT/DGEBA nanocomposite exhibited the best N2 barrier properties, which were about five times those of neat epoxy. Based on a modified Nielsen model, it was clarified that this excellent gas barrier property was due to the homogeneously dispersed lamellas with almost exfoliated structures. The improved morphology and barrier property confirmed the superiority of the adduct, which provides a general method for developing gas barrier nanocomposites.

Sugar-Derived Nanocrystalline Graphite Matrix C/C Composites with Excellent Ablative Resistance at 3000 °C.

Sugars are renewable resources essential to human life, but they are rarely used as raw materials for the industrial production of carbon-based materials, especially for the preparation of carbon fiber-reinforced carbon-matrix (C/C) composites, which are extremely useful for the semiconductor and aerospace sectors. Herein, a method utilizing sugar-derived carbon to replace petrochemicals as dense matrix to preparing C/C composites is reported. The matrix from sugar-derived C/C (S-C/C) composites has a nanocrystalline graphite structure that is highly thermally stable and effectively bonded to the carbon fibers. The mechanical properties of the S-C/C composite are comparable to those prepared from petrochemical sources; significantly, it exhibits a linear ablation rate of 0.03 mm s-1 after 200 s of ablation at 3000 °C in 10 MW m-2 heat flux. This new class of S-C/C is promising for use in a broad range of fields, ranging from semiconductor to aerospace.

4D Printing of Triple-Shape Memory Cyanate Composites Based on Interpenetrating Polymer Network Structures.

The triple-shape memory polymer (TSMP) can be programmed into two temporary shapes (S1 and S2) and shows an ordinal recovery from S2 to S1 and eventually to the permanent shape upon heating, which realizes more complex stimulus-response motions. We introduced a novel strategy for forming triple-shape memory cyanate ester (TSMCE) resins with high strength and fracture toughness via three-step curing, including four-dimensional (4D) printing, UV post-curing, and thermal curing. The obtained TSMCE resins presented two separated glass transition temperature (Tg) regions due to the formation of an interpenetrating polymer network (IPN), which successfully endowed the polymers with the triple-shape memory effect. The two Tg increased with the increasing cyanate ester (CE) prepolymer content; their ranges were 82.7-102.1 °C and 164.4-229.0 °C, respectively. The fracture strain of the IPN CE resin was up to 10.9%. Moreover, the cooperation of short carbon fibers (CFs) and glass fibers (GFs) with the polymer-accelerated phase separation resulted in two well-separated Tg peaks exhibiting better excellent triple-shape memory behaviors and fracture toughness. The strategy for combining the IPN structure and 4D printing provides insight into the preparation of shape memory polymers integrating high strength and toughness, multiple-shape memory effect, and multifunctionality.

Sugar-Derived Isotropic Nanoscale Polycrystalline Graphite Capable of Considerable Plastic Deformation.

Obtaining large plastic deformation in polycrystalline van der Waals (vdW) materials is challenging. Achieving such deformation is especially difficult in graphite because it is highly anisotropic. The development of sugar-derived isotropic nanostructured polycrystalline graphite (SINPG) is discussed herein. The structure of this material preserves the high in-plane rigidity and out-of-plane flexibility of graphene layers and enables prominent plasticity by activating the rotation of nanoscale (5-10 nm) grains. Thus, micrometer-sized SINPG samples demonstrate enhanced compressive strengths of up to 3.0 GPa and plastic strains of 30-50%. These findings suggest a new pathway for enabling plastic deformation in otherwise brittle vdW materials. This new class of nanostructured carbon materials is suitable for use in a broad range of fields, from semiconductor to aerospace applications.

Photosensitive Composite Inks for Digital Light Processing Four-Dimensional Printing of Shape Memory Capture Devices.

High-performance shape memory thermosetting polymers and their composites for four-dimensional (4D) printing are essential in practical applications. To date, most printable thermosets suffer from complicated processes, poor thermodynamic performances, and low printing speed. Here, photosensitive composite inks for fast photocuring printing are developed. The inks consist of epoxy acrylate (EPAc), polyethylene glycol dimethacrylate (PEGDMA), and carbon fillers, which form a firm network structure when exposed to UV light. EPAc is synthesized via addition esterification of epoxy resin and acrylic acid under mild conditions. It is worth noting that raw materials for the reaction are diverse, including not only various epoxy resins but also molecules with epoxy groups. The 4D printing speed of up to 180 mm/h is mainly attributed to the exothermic reaction initiated by free radicals, which accelerates the polymerization of EPAc and PEGDMA. Most importantly, by increasing the exposure time of each layer from 1 s to 3 s during the printing process, the epoxy composite-infilled carbon nanotubes and carbon fibers are printed to ensure the integrity of the microlayer structure. Furthermore, we design a claw-like catcher device based on the above printable composite inks to demonstrate its potential applications in aerospace, such as grasping end-of-service spacecraft or explosive debris. Undoubtedly, 4D printing technology opens up a new portal for the manufacturing of thermoset epoxy composites and complex structures, which make the shape memory thermosetting epoxy resins and their composites possess excellent properties and good engineering application prospects.

ZrW2O8/ZrO2 Composites with Low/Near-Zero Coefficients of Thermal Expansion Fabricated at Ultralow Temperature: An Integration of Hydrothermal Assembly and a Cold Sintering Process.

ZrW2O8/ZrO2 composites with tunable low/near-zero coefficients of thermal expansion (CTE) are promising candidates in several fields including aerospace, precision manufacturing and measurement, electronic circuit, etc., for counteracting the thermal expansion effect. However, bottleneck issues (such as the unstable decomposition of ZrW2O8 phase, manufacturing size limitation, etc.) caused by conventional high-temperature sintering impede the development and application of ZrW2O8/ZrO2. To solve these scientific issues, a methodology integrating hydrothermal assembly with a cold sintering process (CSP) is exploited. The ZrW2O8/ZrO2 composite powders with a mace-like structure, in which the spherical ZrO2 nanoparticles peripherally embed on the rod-like ZrW2O8 matrix particles, are hydrothermally assembled. Then, the relatively dense ZrW2O8/ZrO2 composites with excellent low or even near-zero CTE are successfully achieved by CSP (as low as 190 °C) with a postannealing treatment (550 °C). The evolution of sintering densification, phase composition, and microstructure followed by the fundamental mechanism regarding the hydrothermal assembly of the mace-like structure and densification of CSP are investigated in detail. This research not only effectively overcomes the bottleneck issues of ZrW2O8/ZrO2 via integrating the hydrothermal assembly with the sintering technology at ultralow temperature but also develops a promising prospect for the fabrication of a broader range of metastable functional materials.

[First-principles study of vibrational Raman spectra of amorphous carbon].

The vibrational density of states and nonresonant reduced Raman spectra of amorphous carbon at densities of 2.6, 2.9 and 3.2 g x cm(-3) were calculated by the use of a first-principles plane-wave pesudopotential method. Three structural models were generated by liquid-quench method using Car-Parinello molecular dynamics, their vibrational frequencies and eigenmodes were determined using the linear response approach, and Raman coupling tensors were calculated using the finite electric field method. The calculated results show that the sp3 fraction increases from 50% to 84.4%, the sp2 configuration changes from mainly rings to short chains, the position of the G peak moves to higher frequencies, the intensity ratio of D and G peaks decreases, the position of the T peak moves to lower frequencies and the intensity ratio of T and G peaks increases as density increases from 2.6 to 3.2 g x cm(-3). The authors' calculated Raman spectra show an overall good agreement with experimental spectra. The analysis in terms of atomic vibrations confirms that the G and D peaks both come from sp2 C contribution, G peak is due to the stretching vibration of any pair of sp2 atoms and the T peak is due to the C-C sp3 vibration. The authors' analysis also confirms that the dispersion of G and T peaks is due to bond-length changes. The bond length of chains (olefins) is shorter than that of rings, so their vibrational frequency is higher and the G-peak position moves to higher frequencies with increasing the sp3 fraction. The number of sp3-sp2 type bonds decreases as the sp3 fraction increases. These bonds are shorter than pure sp3-sp3 bonds, hence the T-peak position moves to lower frequencies. The research results provide a theoretic basis for analyzing experimental Raman spectra of amorphous carbon.

A Wearable Supercapacitor Engaged with Gold Leaf Gilding Cloth Toward Enhanced Practicability.

Flexible energy storage devices have attracted wide attention because of the increasing requirement of wearable electronics. However, comfortability, productivity, and feasibility, to name a few, are still far from satisfactory in the current wearable supercapacitors (SCs). This is largely due to the missing of an ideal low-cost flexible substrate/current collector that should not only exhibit high conductivity, but also be compatible with modern textile technologies. Herein, we apply the traditional gilding technique to cloth and successfully convert the cloth to be an excellent current collector which is available at a reasonable cost and compatible with textile technologies. Thanks to the strong electrostatic interaction, we found that a positively charged gold leaf could be laminated on a negatively charged polyester cloth intimately. This substrate could perfectly act as an integrated compact electrode after the electrodeposition of polypyrrole nanorods. The resulting electrode is mechanically strong enough to withstand the tortures of repeated bending, cutting, or puncturing, and is readily assembled into wearable SCs and energy cloth with outstanding practicability, for example, safety and breathability. It is foreseeable that our work will inspire a series design of wearable electronics based on the fascinating gilding art.

Sandwich-structured C/C-SiC composites fabricated by electromagnetic-coupling chemical vapor infiltration.

Carbon fiber (CF) reinforced carbon-silicon carbide (C/C-SiC) composites are one of the most promising lightweight materials for re-entry thermal protection, rocket nozzles and brake discs applications. In this paper, a novel sandwich-structured C/C-SiC composite, containing two exterior C/SiC layers, two gradient C/C-SiC layers and a C/C core, has been designed and fabricated by two-step electromagnetic-coupling chemical vapor infiltration (E-CVI) for a 20-hour deposition time. The cross-section morphologies, interface microstructures and SiC-matrix growth characteristics and compositions of the composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD), respectively. Microstructure characterization indicates that the SiC growth includes an initial amorphous SiC zone, a gradual crystallization of SiC and grow-up of nano-crystal, and a columnar grain region. The sandwich structure, rapid deposition rate and growth characteristics are attributed to the formation of thermal gradient and the establishment of electromagnetic field in the E-CVI process. The composite possesses low density of 1.84 g/cm3, high flexural strength of 325 MPa, and low linear ablation rate of 0.38 µm/s under exposure to 5-cycle oxyacetylene flame for 1000 s at ~1700 °C.

Graphene nanoribbon aerogels unzipped from carbon nanotube sponges.

Graphene nanoribbon aerogels are fabricated by directly unzipping multi-walled carbon nanotube sponges. These fascinating materials have potential applications as high performance nanocomposites and supercapacitor electrodes.

Overtwisted, resolvable carbon nanotube yarn entanglement as strain sensors and rotational actuators.

Introducing twists into carbon nanotube yarns could produce hierarchical architectures and extend their application areas. Here, we utilized such twists to produce elastic strain sensors over large strain (up to 500%) and rotation actuators with high energy density. We show that a helical nanotube yarn can be overtwisted into highly entangled, macroscopically random but locally organized structures, consisting of mostly double-helix segments intertwined together. Pulling the yarn ends completely resolved the entanglement in an elastic and reversible way, yielding large tensile strains with linear change in electrical resistance. Resolving an entangled yarn and releasing its twists could simultaneously rotate a heavy object (30 000 times the yarn weight) for more than 1000 cycles at high speed. The rotational actuation generated from a single entangled yarn produced energy densities up to 8.3 kJ/kg, and maintained similar capacity during repeated use. Our entangled CNT yarns represent a complex self-assembled system with applications as large-range strain sensors and robust rotational actuators.

Highly twisted double-helix carbon nanotube yarns.

The strength and flexibility of carbon nanotubes (CNTs) allow them to be constructed into a variety of innovated architectures with fascinating properties. Here, we show that CNTs can be made into a highly twisted yarn-derived double-helix structure by a conventional twist-spinning process. The double-helix is a stable and hierarchical configuration consisting of two single-helical yarn segments, with controlled pitch and unique mechanical properties. While one of the yarn components breaks early under tension due to the highly twisted state, the second yarn produces much larger tensile strain and significantly prolongs the process until ultimate fracture. In addition, these elastic and conductive double-helix yarns show simultaneous and reversible resistance change in response to a wide range of input sources (mechanical, photo, and thermal) such as applied strains or stresses, light illumination, and environmental temperature. Our results indicate that it is possible to create higher-level, more complex architectures from CNT yarns and fabricate multifunctional nanomaterials with potential applications in many areas.

Adsorption and desorption of antimony acetate on sodium montmorillonite.

The adsorption of antimony acetate (Sb(OAc)(3)) on sodium montmorillonite (Na-MMT) was studied at five different initial concentrations, and data from the adsorption isotherm were modeled using the Langmuir, Freundlich and D-R isotherm equations. The kinetics of adsorption was also discussed using three kinetic models: the pseudo-first-order, the pseudo-second-order and the intraparticle diffusion model. The rate constants of pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetics, and the amount of Sb(OAc)(3) adsorbed at equilibrium were determined. Moreover, the desorption of Sb(OAc)(3) from several kinds of Sb-MMT (Na-MMT was intercalated by antimony acetate) was investigated at room temperature and 180 °C. The results show that according to the maximum amounts of adsorbate and correlation coefficients calculated from the three isotherm equations mentioned above, the corresponding data from adsorption experiments fit fairly well to the Langmuir isotherm. The adsorption data show a good compliance with the pseudo-second-order kinetic model and also follow the intraparticle diffusion model up to 30 min. The equilibrium adsorption capacity of Sb(OAc)(3) on MMT is close to the cation exchange capacity (CEC) of the montmorillonite. The desorption amount of Sb(OAc)(3) is correlated with both the temperature of desorption and the drying temperature of Sb-MMT.