Nanoscale Flexoelectricity

Electromechanical effects are ubiquitous in biological and materials systems. Understanding the fundamentals of these coupling phenomena is critical to devising next‐generation electromechanical transducers. Piezoelectricity has been studied in detail, in both the bulk and at mesoscopic scales. Recently, an increasing amount of attention has been paid to flexoelectricity: electrical polarization induced by a strain gradient. While piezoelectricity requires crystalline structures with no inversion symmetry, flexoelectricity does not carry this requirement, since the effect is caused by inhomogeneous strains. Flexoelectricity explains many interesting electromechanical behaviors in hard crystalline materials and underpins core mechanoelectric transduction phenomena in soft biomaterials. Most excitingly, flexoelectricity is a size‐dependent effect which becomes more significant in nanoscale systems. With increasing interest in nanoscale and nano‐bio hybrid materials, flexoelectricity will continue to gain prominence. This Review summarizes work in this area. First, methods to amplify or manipulate the flexoelectric effect to enhance material properties will be investigated, particularly at nanometer scales. Next, the nature and history of these effects in soft biomaterials will be explored. Finally, some theoretical interpretations for the effect will be presented. Overall, flexoelectricity represents an exciting phenomenon which is expected to become more considerable as materials continue to shrink.     

Ferroelasticity in a metal–organic framework perovskite; towards a new class of multiferroics

A metal–organic framework perovskite, [(CH₂)₃NH₂][Mn(HCOO)₃], exhibits a weakly first order ferroelastic phase transition at ～272 K, from orthorhombic Pnma to monoclinic P2₁/n, and a further transition associated with antiferromagnetic ordering at ～8.5 K. The main structural changes, through the phase transition, are orientational ordering of the azetidium groups and associated changes in hydrogen bonding. In marked contrast to conventional improper ferroelastic oxide perovskites, the driving mechanism is associated with the X-point of the cubic Brillouin zone rather than being driven by R- and M-point octahedral tilting. The total ferroelastic shear strain of up to ～5% is substantially greater than found for typical oxide perovskites, and highlights the potential of the flexible framework to undergo large relaxations in response to local structural changes. Measurements of elastic and anelastic properties by resonant ultrasound spectroscopy show some of the characteristic features of ferroelastic materials. In particular, acoustic dissipation below the transition point can be understood in terms of mobility of twin walls under the influence of external stress with relaxation times on the order of ～10^?7 s. Elastic softening as the transition is approached from above is interpreted in terms of coupling between acoustic modes and dynamic local ordering of the azetidium groups. Subsequent stiffening with further temperature reduction is interpreted in terms of classical strain–order parameter coupling at an improper ferroelastic transition which is close to being tricritical. By way of contrast, there are no overt changes in elastic or anelastic properties near 9 K, implying that any coupling of the antiferromagnetic order parameter with strain is weak or negligible.     

Selective deposition of catalyst nanoparticles using the gravitational force for carbon nanotubes interconnect

The photolithography process has generally been used for the making of catalyst layers used for the synthesis of CNTs due to its comparative ease. However, this method results in the formation of undesirable catalyst particles, which deteriorate the quality of the devices. Therefore, we tried to form a catalyst layer without using any lift-off or wet etching process, especially for the formation of carbon nanotube interconnects. After spin coating the samples, which were previously fabricated with several vias, with an iron-acetate solution, the catalyst layer was pulled down into the bottom of the holes through the force of gravity. We were able to remove the catalyst layer which was coated over undesirable areas, by TMAH (tetramethylammonium hydroxide, N(CH₃)₄OH) treatment. After the catalyst deposition process, we synthesized CNTs and observed them by scanning electron microscopy (SEM).     

Energy efficient model predictive building temperature control

Many systems used in buildings for heating, ventilating, and air-conditioning waste energy because of the way they are operated or controlled. This paper explores the application of model predictive control (MPC) to air-conditioning units and demonstrates that the closed-loop performance and energy efficiency can be improved over conventional approaches. This work focuses on the problem of controlling the vapor compression cycle (VCC) in an air-conditioning system, containing refrigerant which is used to provide cooling. The VCC considered in this work has two manipulated variables that affect operation: compressor speed and the position of an electronic expansion valve. The system is subject to constraints, such as the range of permissible superheat, and also needs to regulate temperature variables to set points. An MPC strategy is developed for this type of system based on linear models identified from data obtained from a first-principles model of the VCC. The MPC strategy incorporates economic measures in the objective function as well as control objectives. Tests are carried out on a simulated VCC system that is linked to a simulation of a realistic building that is developed in the U.S. Department of Energy Computer Simulation Program, EnergyPlus. The MPC demonstrated significantly better tracking control relative to conventional approaches (a reduction of 70% in terms of the integral of squared error for step changes in the temperature set-point), while reducing the VCC energy requirements by 16%. The paper describes the control approach in detail and presents results from the tests.     

Streptococcus thermophilus strains of plant origin as dairy starters: Isolation and characterisation

Streptococcus thermophilus strains have been isolated mainly from dairy environments. To prospect for new strains of S. thermophilus, isolation was made from different plant sources. In this study, 74 plant isolates were characterised as S. thermophilus by a polyphasic approach and by 16S rRNA sequencing. The isolates were further evaluated for their physiological and biochemical properties. Plant isolates exhibited good acid production and varying proteolytic activity. All the isolates showed acetaldehyde and capsular exopolysaccharide (EPS) production and few revealed diacetyl production. In contrast to industrial strains, six isolates were able to ferment galactose and 25 were found to have no urease activity. Both the plant isolates and reference dairy cultures were found to possess similar physiological and biochemical properties and can be considered for developing new starters.     

Localized surface plasmon resonances arising from free carriers in doped quantum dots

Localized surface plasmon resonances (LSPRs) typically arise in nanostructures of noble metals resulting in enhanced and geometrically tunable absorption and scattering resonances. LSPRs, however, are not limited to nanostructures of metals and can also be achieved in semiconductor nanocrystals with appreciable free carrier concentrations. Here, we describe well-defined LSPRs arising from p-type carriers in vacancy-doped semiconductor quantum dots (QDs). Achievement of LSPRs by free carrier doping of a semiconductor nanocrystal would allow active on-chip control of LSPR responses. Plasmonic sensing and manipulation of solid-state processes in single nanocrystals constitutes another interesting possibility. We also demonstrate that doped semiconductor QDs allow realization of LSPRs and quantum-confined excitons within the same nanostructure, opening up the possibility of strong coupling of photonic and electronic modes, with implications for light harvesting, nonlinear optics, and quantum information processing.     

Synthesis of hydrophilic superparamagnetic magnetite nanoparticles via thermal decomposition of Fe(acac), in 80 vol% TREG + 20 vol% TREM

In this paper, we report single step synthesis of hydrophilic superparamagnetic magnetite nanoparticles by thermolysis of Fe(acac)3 and their characterization of the properties relevant to biomedical applications like hyperthermia and magnetic resonance imaging (MRI). Size and morphology of the particles were determined by Transmission electron microscopy (TEM) while phase purity and structure of the particles were identified by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Magnetic properties were evaluated using vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) measurements. The as prepared nanoparticles were found to be superparamagnetic with the blocking temperature of 136 K and were easily suspendable in water. Cytotoxicity studies on human cervical (SiHa), mouse melanoma (B16F10) and mouse primary fibroblast cells demonstrated that up to a dose of 0.1 mg/ml, the magnetite nanoparticles were nontoxic to the cells. To evaluate the feasibility of their uses in hyperthermia and MRI applications, specific absorption rate (SAR) and spin-spin relaxation time (T2) were measured respectively. SAR has been calculated to be above 80 Watt/g for samples with the iron concentration of 5-20 mg/ml at 10 kA/m AC magnetic field and 425 kHz frequency. r2 relaxivity value was measured as 358.4 mM(-1)S(-1) which is almost double as compared to that of the Resovist, a commercially available MRI contrast agent. Thus the as-prepared magnetite nanoparticles may be used for hyperthermia and MRI applications due to their promising SAR and r2 values.     

Amorphous silicon–carbon based nano-scale thin film anode materials for lithium ion batteries

The buffering effect of carbon on the structural stability of amorphous silicon films, used as an anode for lithium ion rechargeable batteries, has been studied during long term discharge/charge cycles. To this extent, the electrochemical performance of a prototype material consisting of amorphous Si thin film (∼250 nm) deposited by radio frequency magnetron sputtering on amorphous carbon (∼50 nm) thin films, denoted as a-C/Si, has been investigated. In comparison to pure amorphous Si thin film (a-Si) which shows a rapid fade in capacity after 30 cycles, the a-C/Si exhibits excellent capacity retention displaying ∼0.03% fade in capacity up to 50 cycles and ∼0.2% after 50 cycles when cycled at a rate of 100 μA/cm² (∼C/2) suggesting that the presence of thin amorphous C layer deposited between the Cu substrate and a-Si acts as a buffer layer facilitating the release of the volume induced stresses exhibited by pure a-Si during the charge/discharge cycles. This structural integrity combined with microstructural stability of the a-C/Si thin film during the alloying/dealloying process with lithium has been confirmed by scanning electron microscopy (SEM) analysis. The buffering capacity of the thin amorphous carbon layer lends credence to its use as the likely compliant matrix to curtail the volume expansion related cracking of silicon validating its choice as the matrix for bulk and thin film battery systems.