Characterizing and controlling infrared phonon anomaly of bilayer graphene in optical-electrical force nanoscopy.

We, for the first time, report the nanoscopic imaging study of anomalous infrared (IR) phonon enhancement of bilayer graphene, originated from the charge imbalance between the top and bottom layers, resulting in the enhancement of E1u mode of bilayer graphene near 0.2 eV. We modified the multifrequency atomic force microscope platform to combine photo-induced force microscope with electrostatic/Kelvin probe force microscope constituting a novel hybrid nanoscale optical-electrical force imaging system. This enables to observe a correlation between the IR response, doping level, and topographic information of the graphene layers. Through the nanoscale spectroscopic image measurements, we demonstrate that the charge imbalance at the graphene interface can be controlled by chemical (doping effect via Redox mechanism) and mechanical (triboelectric effect by the doped cantilever) approaches. Moreover, we can also diagnosis the subsurface cracks on the stacked few-layer graphene at nanoscale, by monitoring the strain-induced IR phonon shift. Our approach provides new insights into the development of graphene-based electronic and photonic devices and their potential applications.

Effects of the Transfer Method and Interfacial Adhesion on the Frictional and Wear Resistance Properties of a Graphene-Coated Polymer.

Graphene is a promising candidate used to reduce friction and wear in micro- and nano-device applications owing to its superior mechanical robustness and intrinsic lubrication properties. Herein, we report the frictional and wear resistance properties of a graphene-coated polymer and how they are affected by fabrication processes. The results show that graphene deposited on a polymer substrate effectively improves both frictional and wear resistance properties, and the degree of improvement significantly depends on the graphene transfer method and interfacial adhesion between graphene and the substrate. Dry-transferred graphene showed better improvement than wet-transferred graphene, and the strong adhesion of graphene achieved by imidazole treatment aided the improvement. A combined analysis of surface morphology and scratch trace shows that the graphene transfer method and graphene adhesion dominate the structural integrity of the transferred graphene, and the graphene/substrate interfacial adhesion plays a decisive role in the improvement of both properties by suppressing the delamination of graphene from the substrate during the nanoscratch test, thereby preventing crack formation in graphene and weakening the puckering effect.

Improved Crystallinity of Graphene Grown on Cu/Ni (111) through Sequential Mobile Hot-Wire Heat Treatment.

Over the past few years, many efforts have been devoted to growing single-crystal graphene due to its great potential in future applications. However, a number of issues remain for single-crystal graphene growth, such as control of nanoscale defects and the substrate-dependent nonuniformity of graphene quality. In this work, we demonstrate a possible route toward single-crystal graphene by combining aligned nucleation of graphene nanograins on Cu/Ni (111) and sequential heat treatment over pregrown graphene grains. By use of a mobile hot-wire CVD system, prealigned grains were stitched into one continuous film with up to ∼97% single-crystal domains, compared to graphene grown on polycrystalline Cu, which was predominantly high-angle tilt boundary (HATB) domains. The single-crystal-like graphene showed remarkably high thermal conductivity and carrier mobility of ∼1349 W/mK at 350 K and ∼33 600 (38 400) cm2 V-1 s-1 for electrons (holes), respectively, which indicates that the crystallinity is high due to suppression of HATB domains.

Structural Integrity Preserving and Residue-Free Transfer of Large-Area Wrinkled Graphene onto Polymeric Substrates.

Wrinkled graphene offers many advantageous features resulting from modifying the structural and physical properties as well as the chemical reactivity of graphene. However, its inadequate transferability to other substrates has limited its usability. This paper reports a roll-based clean transfer approach that enables the damage-free and contamination-free transfer of large-area wrinkled graphene onto polymeric substrates without compromising the integrity of wrinkle structures. The method implements the simultaneous imidazole-assisted etching and doping of chemical vapor-deposited graphene to fabricate multilayer graphene on a thermoplastic polystyrene (PS) substrate coated with a water-soluble poly(4-styrenesulfonic acid) (PSS) sacrificial layer via a roll-based transfer process. The compliant PSS layer affords the conformal contact between the PS substrate and graphene during the wrinkle formation process, enabling the controllable fabrication of graphene wrinkle structures on a large area. The water-soluble properties of PSS simplify the typically difficult separation of wrinkled graphene from the PS substrate after its transfer onto a target substrate. This improves the transferability of wrinkled graphene, rendering the transfer process solvent-free and residue-free. This work demonstrates the feasibility of the formulated method by transferring centimeter-scale wrinkled graphene onto currently used transparent flexible substrates (i.e., polyethylene terephthalate and polydimethylsiloxane). The results indicate that the transferred wrinkled graphene possesses the desirable combination of superior stretchability, optical transmittance, sheet resistance, and electromechanical stability, rendering its suitable application to transparent flexible and stretchable electronics.

Synthesis of Fe-impregnated biochar from food waste for Selenium(â ¥) removal from aqueous solution through adsorption: Process optimization and assessment.

Iron-impregnated food waste biochar (Fe-FWB) was synthesized for Se(Ⅵ) removal from aqueous solution. The effect and interactive effects of different parameters including pyrolysis time, temperature, and Fe concentration were explored using response surface methodology (RSM) to enhance conditions to achieve the highest Se(Ⅵ) removal using Fe-FWB. Pyrolysis time was not significant for Se(Ⅵ) adsorption capacity of Fe-FWB, but temperature and Fe concentration were found to be significant. The highest adsorption was achieved at 3.47 h and 495.0 °C with an Fe concentration of 0.44 M. Fe-FWB synthesized under optimum conditions were used to investigate the kinetic, equilibrium, and thermodynamic adsorption of Se(Ⅵ). Se(Ⅵ) adsorption reached equilibrium within 6 h, and both pseudo-second order and pseudo-first order models were suitable for describing kinetic Se(Ⅵ) adsorption. The Freundlich model was found to suitably fit the equilibrium adsorption data than the Langmuir model. The highest adsorption capacity of Fe-FWB for Se(Ⅵ) was 11.7 mg g-1. Se(Ⅵ) adsorption on Fe-FWB was endothermic and spontaneous. The enthalpy change for Se(Ⅵ) adsorption was 54.4 kJ mol-1, and the entropy change was negative at 15-35 °C. The increment of solution pH from 3 to 11 decreased the Se(Ⅵ) adsorption from 19.2 to 7.4 mg g-1. The impact of interfering anions on Se(Ⅵ) adsorption followed the lineup: HCO3- > HPO42- > SO42- > NO3-. When compared to some adsorbents, the adsorption capacity of Se(Ⅵ) onto Fe-FWB was comparable even at neutral pH and the Fe-FWB was granular. These results indicate that Fe-FWB has prospective application in the removal of Se(Ⅵ) from aqueous solutions.

Simultaneous Improvement in the Strength and Formability of Commercially Pure Titanium via Twinning-induced Crystallographic Texture Control.

The rolling texture formed in the conventional cold rolling process of commercially pure titanium (CP-Ti) for producing a metal sheet significantly limits the potential applications of CP-Ti sheets in various industrial sectors by impairing the formability. Here, we report that by exploiting a twinning-induced crystallographic texture modification, the rolling texture can be weakened and dispersed effectively, leading to a simultaneous improvement in the formability and yield strength. A two-stage cold rolling process was designed with intermediate annealing at a late stage of the conventional cold rolling process to generate deformation twins. The intermediate annealing drove the activation of [Formula: see text] twin and [Formula: see text] - [Formula: see text] double twin in the second stage of the rolling process by removing the internal reaction stress developed in the first stage of the rolling process through recrystallization, and the crystallographic feature of the [Formula: see text] twinned region, i.e., [Formula: see text] twin texture, was effective for type slips and [Formula: see text] twinning to accommodate a through-thickness strain as well as for reducing the planar anisotropy. This enhanced thinning capability and reduced planar anisotropy in the [Formula: see text] twin texture led to an improvement of the formability. We demonstrated the feasibility of the suggested two-stage cold rolling process with ASTM grade 2 CP-Ti.

Abnormal elastic modulus behavior in a crystalline-amorphous core-shell nanowire system.

We investigated the elastic modulus behavior of crystalline InAs/amorphous Al2O3 core-shell heterostructured nanowires with shell thicknesses varying between 10 and 90 nm by conducting in situ tensile tests inside a transmission electron microscope (TEM). Counterintuitively, the elastic modulus behaviors of InAs/Al2O3 core-shell nanowires differ greatly from those of bulk-scale composite materials, free from size effects. According to our results, the elastic modulus of InAs/Al2O3 core-shell nanowires increases, peaking at a shell thickness of 40 nm, and then decreases in the range of 50-90 nm. This abnormal behavior is attributed to the continuous decrease in the elastic modulus of the Al2O3 shell as the thickness increases, which is caused by changes in the atomic/electronic structure during the atomic layer deposition process and the relaxation of residual stress/strain in the shell transferred from the interfacial mismatch between the core and shell materials. A novel method for estimating the elastic modulus of the shell in a heterostructured core-shell system was suggested by considering these two effects, and the predictions from the suggested method coincided well with the experimental results. We also found that the former and latter effects account for 89% and 11% of the change in the elastic modulus of the shell. This study provides new insight by showing that the size dependency, which is caused by the inhomogeneity of the atomic/electronic structure and the residual stress/strain, must be considered to evaluate the mechanical properties of heterostructured nanowires.

Self-Heating-Induced Deterioration of Electromechanical Performance in Polymer-Supported Metal Films for Flexible Electronics.

The retention of electrical performance under the combined conditions of mechanical strain and an electrical current is essential for flexible electronics. Here, we report that even below the critical current density required for electromigration, the electrical current can significantly deteriorate the electromechanical performance of metal film/polymer substrate systems. This leads to a loss of stretchability, and this effect becomes more severe with increasing strain as well as increasing current. The local increase of electrical resistance in the metal film caused by damage, such as localized deformations, cracks, etc., locally raises the temperature of the test sample via Joule heating. This weakens the deformation resistance of the polymer substrate, accelerating the necking instability, and consequently leading to a rapid loss of electrical conductivity with strain. To minimize such a current-induced deterioration of the polymer-supported metal films, we develop and demonstrate the feasibility of two methods that enhance the deformation resistance of the polymer substrate at elevated temperatures: increasing the thickness of the polymer substrate, and utilizing a polymer substrate with a high glass transition temperature.

Silicone-Based Adhesives with Highly Tunable Adhesion Force for Skin-Contact Applications.

A fundamental approach to fabricating silicone-based adhesives with highly tunable adhesion force for the skin-contact applications is presented. Liquid blends consisting of vinyl-multifunctional polydimethylsiloxane (V-PDMS), hydride-terminated PDMS (H-PDMS), and a tackifier composed of a silanol-terminated PDMS/MQ resin mixture and the MQ resin are used as the adhesive materials. The peel adhesion force of addition-cured adhesives on the skin is increased by increasing the H-PDMS molecular weights and the tackifier content, and decreasing the H-PDMS/V-PDMS ratio. There is an inverse relationship between the adhesion force and the Young's modulus. The low-modulus adhesives with a low H-PDMS/V-PDMS ratio exhibit enhanced adhesion properties. The low-modulus adhesives with the high MQ resin content show significantly enhanced adhesion properties. These adhesives exhibit a wide range of modulus (2-499 kPa), and their adhesion force (0.04-5.38 N) is superior to commercially available soft silicone adhesives (0.82-2.79 N). The strong adhesives (>≈2 N) provide sufficient adhesion for fixing the flexible electrocardiogram (ECG) device to the skin in most daily activity. The human ECG signals are successfully recorded in real time. These results suggest that the silicone-based adhesives should be useful as an atraumatic adhesive for the skin-contact applications.

Electromechanical Properties and Spontaneous Response of the Current in InAsP Nanowires.

The electromechanical properties of ternary InAsP nanowires (NWs) were investigated by applying a uniaxial tensile strain in a transmission electron microscope (TEM). The electromechanical properties in our examined InAsP NWs were governed by the piezoresistive effect. We found that the electronic transport of the InAsP NWs is dominated by space-charge-limited transport, with a I ∞ V2 relation. Upon increasing the tensile strain, the electrical current in the NWs increases linearly, and the piezoresistance gradually decreases nonlinearly. By analyzing the space-charge-limited I-V curves, we show that the electromechanical response is due to a mobility that increases with strain. Finally, we use dynamical measurements to establish an upper limit on the time scale for the electromechanical response.

Tracing carbon monoxide uptake by Clostridium ljungdahlii during ethanol fermentation using (13)C-enrichment technique.

Conversion of synthesis gas (CO and H2) to ethanol can be an alternative, promising technology to produce biofuels from renewable biomass. To distinguish microbial utilization of carbon source between fructose and synthesis gas CO and to evaluate biological production of ethanol from CO, we adopted the (13)C-enrichment of the CO substrate and hypothesized that the residual increase in δ(13)C of the cell biomass would reflect the increased contribution of (13)C-enriched CO. Addition of synthesis gas to live culture medium for ethanol fermentation by Clostridum ljungdahlii increased the microbial growth and ethanol production. Despite the high (13)C-enrichment in CO (99 atom % (13)C), however, microbial δ(13)C increased relatively small compared to the microbial growth. The uptake efficiency of CO estimated using the isotope mass balance equation was also very low: 0.0014 % for the low CO and 0.0016 % for the high CO treatment. Furthermore, the fast production of ethanol in the early stage indicated that the presence of sugar in fermentation medium would limit the utilization of CO as a carbon source by C. ljungdahlii.