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Traditional approaches to materials synthesis have largely relied on uniform, equilibrated phases leading to static “condensed-matter” structures (e.g., monolithic single crystals). Departures from these modes of materials design are pervasive in biology. From the folding of proteins to the reorganization of self-regulating cytoskeletal networks, biological materials reflect a major shift in emphasis from equilibrium thermodynamic regimes to out-of-equilibrium regimes. Here, equilibrium structures, determined by global free-energy minima, are replaced by highly structured dynamical states that are out of equilibrium, calling into question the utility of global thermodynamic energy minimization as a first-principles approach. Thus, the creation of new materials capable of performing life-like functions such as complex and cooperative processes, self-replication, and self-repair, will ultimately rely upon incorporating biological principles of spatiotemporal modes of self-assembly. Elucidating fundamental principles for the design of such out-of-equilibrium dynamic self-assembling materials systems is the focus of this issue of MRS Bulletin.
Biological entities are capable of amazing material feats, such as self-organization, self-repair, self-replication, and self-immolation. Indeed, the most intriguing feature of living biomaterials, whether they are tissues, cells, or intracellular structures, is their ability to autonomously sense, decide, and perform work without the need of a project manager. The effect is multiscale—from enzymes to full organisms, each level is capable of such autonomous activities. Further, each scale has similar energy-using units that work together to compose the larger-scale material. For instance, autonomous cells work together to create tissues. In this article, we will discuss some of the outstanding and desirable properties of active biological materials that we might consider mimicking in future materials. We will discuss how such active materials are powered and explore some fundamental lessons we can learn to direct future fundamental scientific inquiries to begin to understand and use these properties to make synthetic, autonomous materials of the future.
The crystal structure of oxybutynin hydrochloride hemihydrate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Oxybutynin hydrochloride hemihydrate crystallizes in space group I2/a (#15) with a = 14.57266(8), b = 8.18550(6), c = 37.16842(26) Å, β = 91.8708(4)°, V = 4421.25(7) Å3, and Z = 8. The compound exhibits X-ray-induced photoreduction of the triple bond. Prominent in the layered crystal structure is the N–H⋅⋅⋅Cl hydrogen bond between the cation and anion, as well as O–H⋅⋅⋅Cl hydrogen bonds from the water molecule and hydroxyl group of the oxybutynin cation. C–H⋅⋅⋅Cl hydrogen bonds also contribute to the crystal energy, and help determine the conformation of the cation. The powder pattern is included in the Powder Diffraction File™ as entry 00-068-1305.
In situ TiB2 particles with polyhedral or near-spherical morphology with more high-index crystal planes exposed were prepared by controlling the addition amount of Sc in commercial pure aluminum matrix. As the content of Sc increased, TiB2 morphology transformed from hexagonal platelets to polyhedral or near-spherical morphology with a decrease in particle size. In the present paper, a simple method to prepare near-spherical in situ TiB2 particles in Al matrix was explored and it was found that the reinforcement distribution was improved significantly. The different growth mechanism of TiB2 particles in Al and Al–Sc systems was discussed. The key reason for the morphology evolution was that the Sc was preferentially adsorbed on ${\bf \left\{ {1{\bf \overline{2}}12} \right\}}$, ${\bf \left\{ {11\overline{2}0} \right\}}$, and ${\bf \left\{ {10\overline{1}1} \right\}}$ which would inhibit the growth of these faces effectively and retain a lower-energy state of the polyhedral or quasispherical TiB2 particles in Al–Sc systems.
We report the synthesis of a novel polymer gel electrolyte primarily based on cellulose extracted from wood along with gelatin, polyacrylic acid (PAA) and potassium hydroxide (KOH) added as additives in minute amounts in various stages. We also study and report the variation of ionic conductivity with variation of various additives. We found that, with variation of additives to hydrogel, its stability and degree of crystallinity are varied. The results were confirmed using x-ray diffraction and Fourier transform infrared spectra studies. An average best ionic conductivity of 96.89mS/cm was reported for a hydrogel: gelatin: PAA: KOH system, which is one of the best reported values of ionic conductivity for gel electrolytes.
A principal mode of corrosion in combustion or fuel cell environments is the formation of volatile hydroxides and oxyhydroxides from metal or oxide surfaces at high temperatures. It is important to determine the degree of volatility and accurate thermodynamic properties for these hydroxides. Significant gaseous metal hydroxides/oxyhydroxides are discussed, along with available experimental and theoretical methods of characterizing species and determining their thermodynamic properties.
The effects of specimen size, Hall–Petch (H-P) grain or subgrain size, particle size plus spacing, and crack size on the yield strength, plastic deformation, and fracturing properties of crystalline materials are described on a dislocation mechanics basis. The size effects are assessed at relevant macro- and/or micro-and/or nano-scale dimensions; in the latter case, at the upper-limiting strength levels. The description is applied mostly to face-centered cubic (FCC), body-centered cubic (BCC), and hexagonal close-packed (HCP) metals but also involves grain size/particle size–dependent (composite) steel material behaviors. Competition is described for the role of dislocation pile-ups versus hole-joining mechanisms for ductile failure. Grain size–dependent microhardness and strain rate sensitivity measurements are presented for nano-grain size strengthening and grain size weakening, respectively. An intrinsic size effect is demonstrated for silicon crystal nano-indentation hardness testing, which, on microscale loading, leads to evaluation of crack size dependence and, for polycrystalline alumina, to associated H-P behavior for the fracture mechanics stress intensity.
Asymmetric membranes present promising characteristics for wound dressing applications. A porous structure uptakes the wound exudate, whereas an occlusive layer (upper film) inhibits the microbial penetration and prevents an excessive loss of water. Konjac glucomannan (KGM) is a natural polysaccharide that has been investigated as wound dressings in the form of films, sponges, and hydrogels due to its flexibility, swelling capacity, biocompatibility, and low cost. However, there are no studies on literature regarding the development of KGM asymmetric membranes. In this study, we investigated a new casting–freezing process for the production of KGM asymmetric membranes. The scanning electron microscopy and thermogravimetric analyses indicated an asymmetric morphology and a good thermal stability of the membrane samples, respectively. Moreover, biological, mechanical, and fluid-handling capacity tests showed that the membrane is biocompatible and resistant to handling structure, which was also able to retain the ideal moist conditions for wound healing.
This study reports the fabrication of high mass loading (32 mg/cm2) electrodes of niobium pentoxide (Nb2O5) nanoparticles and carbon nanotubes (CNTs) using a facile procedure. The as-obtained Nb2O5 nanoparticles by microwave-assisted hydrothermal synthesis presented pseudohexagonal (TT) phase, and when exposed to the thermal treatment, the Nb2O5 nanoparticles changed to orthorhombic (T) phase. Distinct morphologies were obtained, which exhibited a specific surface area of 216 m2/g and 47 m2/g to pseudohexagonal and orthorhombic phases, respectively. Cyclic voltammetry and electrochemical impedance spectroscopy techniques were performed in a three-electrode system using 1 M Li2SO4 as electrolyte with a potential window of 0–0.9 V (versus standard calomel electrode). Both materials showed capacitive behavior with a specific capacitance of 0.11 F/cm2 and 0.09 F/cm2 to nanocomposites CNT + TT-Nb2O5 and CNT + T-Nb2O5 at 2 mV/s, respectively. Thus, an efficient, simple, and promising process to produce electrodes for supercapacitors was demonstrated.
CdS/ZnS core shell quantum dots (QDs) were synthesized and functionalized by methionine and characterized by standard techniques. The prior QD-based phytotoxicity assay was helpful to find out the maximum tolerant level of the plant cells. The successful transport and phytotoxic mechanism of QDs were elaborated in detail. Methionine functionalities on the QDs were helpful in specific binding of QDs with the nucleus of stomata in plant cells. Target specific interaction with the nucleus of stomata cells was a novel breakthrough that can be used in many biologic applications.
Direct urea fuel cells were fabricated using CuNi-plated polymer cloth for anode catalyst and current collector, and Pt-black for cathode catalyst. The output power was significantly enhanced by coating the CuNi cloth with a conducting polymer, poly(3,4-ethylenedioxythiophene)polystyrene sulfonate (PEDOT*PSS). The open circuit voltage, 0.80 V and the maximum output power, 3.0 mW/cm2 were obtained for the fuel of 0.5 M urea water solution under ambient conditions. Improvement over the cell structure demonstrated to lighten a light emitting diode.
Nickel thin films were prepared by electroless plating in a foam of electrolyte generated by bubbling nitrogen into a hypophosphite-based electroless plating solution added with surfactants of sulfuric acid monododecyl ester sodium salt and ammonium pentadecafluorooctanoate (APFO). Ferroxyl test revealed that the films deposited in foam had substantially higher corrosion resistance than those deposited in liquid. Even with a film thickness of only 1.5 µm, the fraction of corroded area was as small as 0.002% when the film was deposited in the foam. The notable improvement in the corrosion resistance was made possible by adding APFO as the surfactant.
By electron-beam (e-beam) melting, we prepared 0.4 wt% carbon-infused copper (CuCv4), and a copper control without carbon addition (CuCv0). Scanning electron microscopy and helium ion microscopy (HIM) were performed on the as-solidified surface, fracture surface, and ion-polished surface of the CuCv4 sample. The results revealed that graphitic carbon flakes cover the as-solidified surface, and carbon nanoparticles and clusters exist in the fracture and ion-polished surfaces. HIM on the ion-polished surface revealed a unique ripple-shaped feature, which is possibly associated with the infusion of carbon nanoribbons in the copper matrix. The bulk densities were measured to be 8.86 and 8.53 g/cm3, which correspond to relative densities of 98.9% and 96.4% for the CuCv0 and CuCv4 samples, respectively. In addition, apparent electrical conductivities were measured to be 56.9 and 57.5 MS/m, respectively, for the e-beam melted CuCv0 and CuCv4 samples. These values correspond to true electrical conductivities of 100.5% IACS (International Annealed Copper Standard) and 107.4% IACS after correction for the porosity. Our results reveal remarkable promise of using covetic copper for the next generation conductors in energy applications from microelectronic devices to high-power transmission cables.
The finite element simulations show that non-equibiaxial residual stresses (RS) can shift the load–depth curve from the unstressed curve and cause elliptical remnant indentation in spherical indentation. Thus the relative load change between stressed and unstressed samples and the asymmetry of elliptical remnant indentation were employed as characteristic parameters to evaluate the magnitude and directionality of RS. Through theoretical and numerical analysis, the effects of RS on indentation load and remnant impression as well as the affect mechanism were systematically discussed. Finally, two equations which could provide foundations for establishing spherical indentation method to evaluate non-equibiaxial RS were obtained.
We previously demonstrated that electrode architectures comprising nanoscale birnessite-like MnOx affixed to three-dimensional carbon nanofoam (CNF) scaffolds offer performance advantages when used as cathodes in rechargeable zinc-ion cells. To discern chemical and physical changes at the MnOx@CNF electrode upon deep charge/discharge in aqueous Zn2+-containing electrolytes, we deploy electroanalytical methods and ex situ characterization by microscopy, elemental analysis, x-ray photoelectron spectroscopy, x-ray diffraction, and x-ray pair distribution function analyses. Our findings verify that redox processes at the MnOx are accompanied by reversible precipitation/dissolution of crystalline zinc hydroxide sulfate (Zn4(OH)6(SO4)·xH2O), mediated by the more uniformly reactive electrode structure inherent to the CNF scaffold.
The glass surfaces used for optical devices are necessary to have high transparency. Here we propose to take advantage of tube-like SiO2 textures to trap lubricant liquid inside aiming to prepare novel slippery liquid-infused porous surfaces (SLIPS). As a consequence, SLIPS with high transparency were synthesized on glass substrate successfully. The capillary action of unique tubular structure induces the ion migration of adjacent Krytox 100, thus endowing SLIPS with the self-healing property. Moreover, the remarkable slip behavior enables these surfaces to possess the self-cleaning and anti-biofouling performances. The current work might provide a promising candidate for long-term transparent optical devices.
A review is given of the future device processing needs for Ga2O3 power electronics. The two main devices employed in power converters and wireless charging systems will be vertical rectifiers and metal oxide semiconductor field effect transistors (MOSFETs). The rectifiers involve thick epitaxial layers on conducting substrates and require stable Schottky contacts, edge termination methods to reduce electric field crowding, dry etch patterning in the case of trench structures, and low resistance Ohmic contacts in which ion implantation or low bandgap interfacial oxides are used to minimize the specific contact resistance. The MOSFETs also require spatially localized doping enhancement for low source/drain contact resistance, stable gate insulators with acceptable band offsets relative to the Ga2O3 to ensure adequate carrier confinement, and enhancement mode capability. Attempts are being made to mitigate the absence of p-type doping capability for Ga2O3 by developing p-type oxide heterojunctions with n-type Ga2O3. Success in this area would lead to minority carrier devices with better on-state performance and a much-improved range of functionality, such as p-i-n diodes, Insulated Gate Bipolar Transistors, and thyristors.
The formation of nanosized porous oxide layers on titanium (Ti) by asymmetric alternating current anodizing in sulfuric acid has been studied using electrochemical techniques. In order to prevent spark discharge at Ti electrode upon its anodization in 1.0 M H2SO4 solution, the magnitude of the cathodic current is reduced using a special electrical circuit consisting of a variable resistor and two diodes. The unique surface treatment approach gives rise to the formation of nanosized porous layer in a very short period of time and without spark discharge. The surface of porous layers thus obtained has in vitro apatite-forming ability.
Ferroelectric single-crystal-architecture-in-glass is a new class of metamaterials that would enable active integrated optics if the ferroelectric behavior is preserved within the confines of glass. We demonstrate using lithium niobate crystals fabricated in lithium niobosilicate glass by femtosecond laser irradiation that not only such behavior is preserved, the ferroelectric domains can be engineered with a DC bias. A piezoresponse force microscope is used to characterize the piezoelectric and ferroelectric behavior. The piezoresponse correlates with the orientation of the crystal lattice as expected for unconfined crystal, and a complex micro- and nano-scale ferroelectric domain structure of the as-grown crystals is revealed.