Material Design for 3D Multifunctional Hydrogel Structure Preparation

Hydrogels are recognized as one of the most promising materials for e-skin devices because of their unique applicable functionalities such as flexibility, stretchability, biocompatibility, and conductivity. Beyond the excellent sensing functionalities, the e-skin devices further need to secure a target-oriented 3D structure to be applied onto various body parts having complex 3D shapes. However, most e-skin devices are still fabricated in simple 2D film-type devices, and it is an intriguing issue to fabricate complex 3D e-skin devices resembling target body parts via 3D printing. Here, a material design guideline is provided to prepare multifunctional hydrogels and their target-oriented 3D structures based on extrusion-based 3D printing. The material design parameters to realize target-oriented 3D structures via 3D printing are systematically derived from the correlation between material design of hydrogels and their gelation characteristics, rheological properties, and 3D printing processability for extrusion-based 3D printing. Based on the suggested material design window, ion conductive self-healable hydrogels are designed and successfully applied to extrusion-based 3D printing to realize various 3D shapes.     

Micron-Scale Soft Actuators Fabricated from Multi-Shell Polystyrene Particle-Gold Nanoparticle Nanohybrids

Actuators made of soft matter are needed for a variety of fields ranging from biomedical devices to soft robotics to microelectromechanical systems. While there are a variety of excellent methods of soft actuation known, the field is still an area of intense research activity as new niches and needs emerge with new technology development. Here, a soft actuation system is described, based on a core-multi-shell particle, which moves via photothermal expansion. The system consists of a novel polystyrene-based thermally expandable microsphere, with a secondary shell of a silicate-silane graft copolymer, to which gold nanoparticles are covalently linked. The gold nanoparticles act as photothermal nano-transducers, converting light energy into the thermal energy necessary for microsphere expansion, which in turn results in material movement. Actuation is shown in isolated particles in thermal and photothermal regimes using metal ceramic heaters or 520 nm laser illumination, respectively. Macroscale actuation is demonstrated by making a composite material of particles suspended in the transparent elastomer polydimethylsiloxane. The sample demonstrates an inchworm-like movement by starting from an arched geometry. Overall, this work describes a new particle-based actuation method for soft materials, and demonstrates its utility in driving the movement of a composite elastomer.     

Synergistic Flame Retardant Effects of Carbon Nanotube-Based Multilayer Nanocoatings

In an effort to develop highly functionalized flame retardant materials, hybrid nanocoatings are prepared by alternately depositing a positively charged polyaniline (PANi) and negatively charged montmorillonite (MMT) using the layer-by-layer (LbL) assembly technique. Carbon nanotubes (CNTs) are employed in polymer nanocomposites as effective reinforcement, where nanotubes are stabilized in MMT aqueous solution. The 3D structure and high density of CNTs deposited in the PANi/CNTs-MMT multilayers produce thicker and heavier coatings in comparison to the LbL assemblies without CNTs. Vertical and horizontal flame testing show that the incorporation of CNTs improves fire resistance. Additionally, cone calorimetry reveals that stacking two nanomaterials (MMT and CNTs) in a single coating shows a significant reduction in peak heat release rate (up to 51%), total smoke release (up to 47%), and total heat release (up to 37%) for the polyurethane foam. The enhancement of flame retardancy is attributed to a synergistic effect; MMT serves as a physical barrier that retards the diffusion of heat and gas. The addition of CNTs strengthens the thermal stability and high char yield. These results, coupled with the simplicity with which the LbL deposition is applied, present a viable alternative to halogen-free flame retardant nanocoatings to natural and synthetic fibers.     

An Autophagy-Disrupting Small Molecule Promotes Cancer Cell Death via Caspase Activation

A novel autophagy inhibitor, autophazole (Atz), which promoted cancer cell death via caspase activation, is described. This compound was identified from cell-based high-content screening of an imidazole library. The results showed that Atz was internalized into lysosomes of cells where it induced lysosomal membrane permeabilization (LMP). This process generated nonfunctional autolysosomes, thereby inhibiting autophagy. In addition, Atz was found to promote LMP-mediated apoptosis. Specifically, LMP induced by Atz caused release of cathepsins from lysosomes into the cytosol. Cathepsins in the cytosol cleaved Bid to generate tBid, which subsequently activated Bax to induce mitochondrial outer membrane permeabilization (MOMP). This event led to cancer cell death via caspase activation. Overall, the findings suggest that Atz will serve as a new chemical probe in efforts aimed at gaining a better understanding of the autophagic process.     

Implementation of pole placement adaptive controller for force control of non-minimum phase end milling operations

The design and implementation of a pole placement adaptive controller are discussed for force control of the end milling process. The end milling process considered is a non-minimum phase system whose computational delay exceeds one half of the control interval. The internal model principle is included in the controller design to ensure a zero steady-state tracking error. Experimental results show that the pole placement adaptive controller is effective for force control of the non-minimum phase end milling operation and the closed-loop control system is stable over a wide range of cutting conditions.     

Nucleation of highly oriented diamond on silicon

Highly oriented diamond particles were deposited on the mirror-polished (100) silicon substrates in the belljar type microwave plasma deposition system. The diamond films were deposited by a three-step process consisting of carburization, bias-enhanced nucleation and growth. The bias-enhanced nucleation was performed under the deposition conditions such as 2-3% of methane concentration in hydrogen, 1333-2666 Pa of total pressure, the negative bias voltage below 200V and the substrate temperature of 1073 K. By adjusting the geometry of the substrate and substrate holder, very dense disc-shaped plasma was formed on the substrate when the bias voltage was below 200V. As characterized by transmission electron microscopy (TEM), almost perfectly oriented diamond particles were obtained only in this dense plasma. From the results of the optical emission spectra of disc-shaped dense plasma, it was found that the concentrations of atomic hydrogen and hydrocarbon radicals were increased with negative bias voltage. As a result, it was suggested that the highly oriented diamonds were obtained by the combination of the high dose of hydrocarbon radicals and the increased hydrogen etching effects.     

Reactions at the corroding nickel electrode in molten sodium carbonate under CO/CO2 atmosphere

Anodic reactions at the CO, CO₂|Ni electrode in molten sodium carbonate at 1000°C are examined in detail. Experimental polarization curves are fitted via a computer graphics procedure to a model employing five anodic reactions with activation, concentration and resistance polarization, and passivation. The resultant empirical parameters are interpreted in terms of absolute rate expressions describing possible anodic reactions. Three of the anodic reactions are found to be in accord with the findings at inert electrodes by previous investigators, i.e. oxidation of CO by two mechanisms and oxidation of carbonate, while the cathodic reaction is consistent with reduction of CO₂. The remaining two anodic reactions were associated with the oxidation of nickel to Ni²⁺ with formation of a NiO film above a passivation potential, and, at higher anodic overpotentials, oxidation of NiO to a higher oxide, e.g. Ni₂O₃. There is an indication of the formation of a third oxide at still higher anodic overpotentials.     

Microstructural evidence for short-circuit oxygen diffusion paths in the oxidation of a dilute Ni-Cr alloy

A comparative study of high-temperature oxidation of Ni containing 1 at.% Cr and pure Ni was carried out. Instead of the conventional kinetics study using thermogravimetry, a microlithographic marker experiment was designed. Observation of the markers using cross-sectional TEM and SEM has revealed striking differences in the scale morphology, microstructures, and oxidation mechanisms between pure Ni and the Cr-doped Ni substrates. In particular, the results suggest that a small addition of Cr promotes significant inward transport of oxygen. Marker experiments revealed that NiO grown on pure Ni is wholly attributable to outward-cation diffusion. In contrast, NiO grown on Ni–1 at.% Cr exhibited formation of a substantial inner layer having a submicron grain size, established by the markers to have formed from oxygen ingress. For pure Ni, voids were observed to be distributed only within oxide grains. In contrast, for Ni containing 1 at.% Cr, elongated pores formed extensively along oxide-grain boundaries. Formation of new fine-grain oxide in these pores was observed to have sometimes completely resealed the void. It is, therefore, proposed that the transport of oxygen in the case of oxide scale grown on Ni–1 at.% Cr occurs via voids (pores) formed by vacancy coalescence at the grain boundaries.     

Carbon-nanotube-based electrochemical double-layer capacitor technologies for spaceflight applications

Electrochemical double-layer capacitors, or supercapacitors, have tremendous potential as high-power energy sources for use in low-weight hybrid systems for space exploration. Electrodes based on single-wall carbon nanotubes (SWCNTs) offer exceptional power and energy performance due to the high surface area, high conductivity, and the ability to functionalize the SWCNTs to optimize capacitor properties. This paper will report on the preparation of electrochemical capacitors incorporating SWCNT electrodes and their performance compared with existing commercial technology. Preliminary results indicate that substantial increases in power and energy density are possible. The effects of nanotube growth and processing methods on electrochemical capacitor performance is also presented. The compatibility of different SWCNTs and electrolytes was studied by varying the type of electrolyte ions that accumulate on the high-surface-area electrodes. For more information, contact W.J. Ready, Georgia Tech Research Institute, 925 Dalney St., Atlanta, GA 30332; (404) 385-4497; fax (404) 894-0580; e-mail jud.ready@gtri.gatech.edu.     

Low temperature OMVPE growth of ZnSe withTertiary-butyl allyl selenide and dimethylzinc-triethylamine

The growth of high quality ZnSe by organometallic vapor phase epitaxy (OMVPE) has been investigated fortertiary-butyl allyl selenide (tBASe), combined with dimethylzinc-triethylamine (DMZn : NEt₃). Single crystalline ZnSe films were grown on GaAs at temperature as low as 350°C with a reasonable growth rate (~1 µm/h). Secondary ion mass spectrometry (SIMS) spectra show a negligible carbon incorporation in ZnSe films from tBASe even at high VI/II ratio, in contrast the carbon concentration of 10²¹ cm^-3 in ZnSe films grown from diallyl selenide (DASe)and methylallylselenide (MASe). Good surface morphology, crystalline and interface quality of ZnSe on (001) GaAs are confirmed by scanning electron microscopy, double crystal diffractometry (DCD) and Rutherford backscattering spectrometry (RBS). Photoluminescence at 10K shows sharp near-band-edge excitonic spectra.