Effect of Secondary Phase on Passivation Layer of Super Duplex Stainless Steel UNS S 32750: Advanced Safety of Li-Ion Battery Case Materials.

Aluminum, traditionally the primary material for battery casings, is increasingly being replaced by UNS S 30400 for enhanced safety. UNS S 30400 offers superior strength and corrosion resistance compared to aluminum; however, it undergoes a phase transformation owing to stress during processing and a lower high-temperature strength. Duplex stainless steel UNS S 32750, consisting of both austenite and ferrite phases, exhibits excellent strength and corrosion resistance. However, it also precipitates secondary phases at high temperatures, which are known to form through the segregation of Cr and Mo. Various studies have investigated the corrosion resistance of UNS S 32750; however, discrepancies exist regarding the formation and thickness of the passivation layer. This study analyzed the oxygen layer on the surface of UNS S 32750 after secondary-phase precipitation. The microstructure, volume fraction, chemical composition, and depth of O after the precipitation of the secondary phases in UNS S 32750 was examined using FE-SEM, EDS, EPMA and XRD, and the surface chemical composition and passivation layer thickness were analyzed using electron probe microanalysis and glow-discharge spectroscopy. This study demonstrated the segregation of alloy elements and a reduction in the passivation-layer thickness after precipitation from 25 µm to 20 µm. The findings of the analysis aid in elucidating the impact of secondary-phase precipitation on the passivation layer.

Study of Precipitated Secondary Phase at 700 °C on the Electrochemical Properties of Super Duplex Stainless Steel AISI2507: Advanced High-Temperature Safety of a Lithium-Ion Battery Case.

Super duplex stainless steel (SDSS) is a suitable structural material for various engineering applications due to its outstanding strength and corrosion resistance. In particular, its high-temperature strength can enhance the safety of electronic products and cars. SDSS AISI2507, known for its excellent strength and high corrosion resistance, was analyzed for its microstructure and electrochemical behavior at the ignition temperature of Li-ion batteries, 700 °C. At 700 °C, AISI2507 exhibited secondary phase precipitation values of 1% and 8% after 5 and 10 h, respectively. Secondary phase precipitation was initiated by the expansion of austenite, forming sigma, chi, and CrN phases. The electrochemical behavior varied with the fraction of secondary phases. Secondary phase precipitation reduced the potential (From -0.25 V to -0.31 V) and increased the current density (From 8 × 10-6 A/cm2 to 3 × 10-6 A/cm2) owing to galvanic corrosion by sigma and chi. As the fraction of secondary phases increased (From 0.0% to 8.1%), the open circuit potential decreased (From -0.25 V to -0.32 V). Secondary phase precipitation is a crucial factor in reducing the corrosion resistance of SDSS AISI2507 and occurs after 1 h of exposure at 700 °C.

Glutamate oxidase sheets-Prussian blue grafted amperometric biosensor for the real time monitoring of glutamate release from primary cortical neurons.

Glutamate (GLU) is a primary excitatory neurotransmitter, and its dysregulation is associated with several neurodegenerative disorders. A major challenge in GLU estimation is the existence of other biomolecules in the brain that could directly get oxidized at the electrode. Hence, highly selective electroenzymatic biosensors that enable rapid estimation of GLU are needed. Initially, a copolymer, poly(2-dimethylaminoethyl methacrylate- styrene) was synthesized through reversible addition-fragmentation chain transfer polymerization to noncovalently functionalize reduced graphene oxide (rGO), named DS-rGO. Glutamate oxidase macromolecule immobilized DS-rGO formed enzyme nanosheets, which was drop-coated over Prussian blue electrodeposited disposable electrodes to fabricate the GLU biosensor. The interconnectivity between the enzyme nanosheets and the Prussian blue endows the biosensor with enhanced conductivity and electrochemical activity. The biosensor exhibited a linearity: 3.25-250 µM; sensitivity: 3.96 µA mM-1 cm-2, and a limit of detection: 0.96 µM for GLU in the Neurobasal Medium. The biosensor was applied to an in vitro primary rat cortical model to discriminate GLU levels in Neurobasal Medium, before and after KCl mediated depolarization, which provides new insights for elucidating neuronal functioning in the brain.

Effect of Secondary Phase on Electroless Ni Plating Behaviour of Super Duplex Stainless Steel SAF2507 for Advanced Li-Ion Battery Case.

The development of Li-ion battery cases requires superior electrical conductivity, strength, and corrosion resistance for both cathode and anode to enhance safety and performance. Among the various battery case materials, super duplex stainless steel (SDSS), which is composed of austenite and ferrite as two-phase stainless steel, exhibits outstanding strength and corrosion resistance. However, stainless steel, which is an iron-based material, tends to have lower electrical conductivity. Nevertheless, nickel-plating SDSS can achieve excellent electrical conductivity, making it suitable for Li-ion battery cases. Therefore, this study analysed the plating behaviour of SDSS plates after nickel plating to leverage their exceptional strength and corrosion resistance. Electroless Ni plating was performed to analyse the plating behaviour, and the plating behaviour was studied with reference to different plating durations. Heat treatment was conducted at 1000 °C for one hour, followed by cooling at 50 °C/s. Post-heat treatment, the analysis of phases was executed using FE-SEM, EDS, and EPMA. Electroless Ni plating was performed at 60-300 s. The plating duration after the heat treatment was up to 300 s, and the behaviour of the materials was observed using FE-SEM. The phase analysis concerning different plating durations was conducted using XRD. Post-heat treatment, the precipitated secondary phases in SAF2507 were identified as Sigma, Chi, and CrN, approximating a 13% distribution. During the electroless Ni plating, the secondary phase exhibited a plating rate equivalent to that of ferrite, entirely plating at around 180 s. Further increments in plating time displayed growth of the plating layer from the austenite direction towards the ferrite, accompanied by a reduced influence from the substrate. Despite the differences in composition, both the secondary phase and austenite demonstrated comparable plating rates, showing that electroless Ni plating on SDSS was primarily influenced by the substrate, a finding which was primarily confirmed through phase analysis.

Emerging Trends in nanostructured materials-coated screen printed electrodes for the electrochemical detection of hazardous heavy metals in environmental matrices.

Heavy metal ions (HMIs) have become a significant contaminant in recent years. The increase in heavy metal pollution is a serious situation, requiring progressively robust, fast sensing, highly sensitive, and suitable techniques for heavy metal detection. Compared to other classical analytical methods, electroanalytical techniques, especially stripping voltammetric techniques with modified screen-printed electrodes (SPEs), have several advantages, such as fast sensing, great sensitivity, specificity, and long-time stability. Therefore, these techniques are more suitable for HMI detection. In this review, the nanostructured materials used to coat SPEs for the electrochemical determination of HMI are summarized. Additionally, the electrode fabrication method, modification steps, and electroanalytical study of these materials are systematically discussed. Hence, this review will support the researchers in precisely evaluating the electrochemical HMIs detection through highly sensitive stripping voltammetric techniques using SPE modified with nanostructured carbon and their allotropes, metal, metal oxides and their nanocomposites as sensor materials. Moreover, modified electrodes real time detection of HMIs in different food and environmental samples were briefly discussed.

Fabrication of S and O-incorporated graphitic carbon nitride linked poly(1,3,4-thiadiazole-2,5-dithiol) film for selective sensing of Hg2+ ions in water, fish, and crab samples.

Screen-printed carbon electrodes (SPCE) were modified with sulfur and oxygen-incorporated graphitic carbon nitride (S, O-GCN) linked poly(1,3,4-thiadiazole-2,5-dithiol) film (PTD) through thioester linkage. The promising interaction between the Hg2+ and modified materials containing sulfur as well as oxygen through strong affinity was studied. This study was utilized for the electrochemical selective sensing of Hg2+ ions by differential pulse anodic stripping voltammetry (DPASV). After, optimizing the different experimental parameters, S, O-GCN@PTD-SPCE was used to improve the electrochemical signal of Hg2+ ions and achieved a concentration range of 0.05-390 nM with a detection limit of 13 pM. The real-world application of the electrode was studied in different water, fish, and crab samples and their obtained results were confirmed with Inductive Coupled Plasma - Optical Emission Spectroscopy (ICP-OES) studies. Additionally, this work established a facile and consistent technique for enhancing the electrochemical sensing of Hg2+ ions and discusses various promising applications in water and food quality analysis.

Embedded Oxidized Ag-Pd-Cu Ultrathin Metal Alloy Film Prepared at Low Temperature with Excellent Electronic, Optical, and Mechanical Properties.

Most transparent conducting materials are based on Sn:In2O3 (ITO). When applied onto flexible substrates, ITO can be prepared in an oxide-metal-oxide (OMO) configuration, typically ITO/Ag/ITO, where the ductility of the embedded metal layer is intended to reduce the mechanical brittleness and improve the electrical conductivity of the OMO multilayer. Hitherto, the lower limit of the thickness of the Ag layer has been limited by the percolation threshold, which limits the Ag layer to be thicker than ∼10 nm to avoid agglomeration and to ensure conductivity and structural stability. Metal layers of thicknesses below 10 nm are, however, desirable for obtaining OMO coatings with better optical properties. It is known that agglomeration of the metal layer can, to some extent, be suppressed when substituting Ag by an Ag-Pd-Cu (APC) alloy. APC-based OMO films exhibit excellent optical and electrical properties, but still continuous APC films well below 10 nm thickness cannot be achieved. In this work we demonstrate that controlled oxidation of APC results in smooth, ultrathin APC:O continuous coatings (of thickness ∼5 nm) on ITO-coated PET substrates. Moderate oxidation yields superficial PdOx formation, which suppresses Ag agglomeration, while still maintaining excellent conductivity. On the other hand, extensive oxidation of APC leads to extensive Pd oxide nucleation deteriorating the conductivity of the film. The ITO/APC:O/ITO films exhibit low resistivity, attributed to a high Hall mobility associated with suppressed agglomeration, good stability in high humidity/temperature environments, superior transmittance in the visible and infrared region, and excellent mechanical bending properties, thus providing new opportunities for fabricating superior transparent conducting coatings on polymer substrates.

Hydrogen-driven dramatically improved mechanical properties of amorphized ITO-Ag-ITO thin films.

An oxide/metal/oxide (OMO) multi-structure, which has good electrical, optical, and mechanical stability, was studied as a potential replacement of polycrystalline In-Sn-O (ITO). However, the degradation of mechanical properties caused by the polycrystalline structure of the top layer forming on the polycrystalline metal layer needs to be improved. To address this issue, we introduced hydrogen in the oxide layers to form a stabilized amorphous oxide structure despite it being deposited on the polycrystalline layer. An ITO/Ag/ITO (IAI) structure was used in this work, and we confirmed that the correct amount of hydrogen introduction can improve mechanical stability without any deterioration in optical and electrical properties. The hydrogen presence in the IAI as intended was confirmed, and the assumption was that the hydrogen suppressed the formation of microcracks on the ITO surface due to low residual stress that came from decreased subgap level defects. This assumption was clearly confirmed with the electrical properties before and after dynamic bending testing. The results imply that we can adjust not only IAI structures with high mechanical stability due to the right amount of hydrogen introduction to make stabilized amorphous oxide but also almost all oxide/metal/oxide structures that contain unintended polycrystalline structures.

Polymer-dispersed reduced graphene oxide nanosheets and Prussian blue modified biosensor for amperometric detection of sarcosine.

A new disposable amperometric biosensor for sarcosine (Sar, a biomarker for prostate cancer) was designed based on screen-printed carbon electrodes, Prussian blue, polymer dispersed reduced graphene oxide (P-rGO) nanosheets, and sarcosine oxidase (SOx). Poly(sodium 4-styrenesulfonate-r-LAHEMA) denoted as PSSL was newly synthesized as dispersant for rGO. The P-rGO was utilized for SOx immobilization, the sulfonate and disulfide functionalities in PSSL enable physical adsorption of SOx and its bioactivity and stability properties were improved. The biosensor was optimized by various enzyme concentration, applied potential, and operating pH. Under the optimized conditions, the biosensor exhibited maximum current responses within 5 s at an applied potential of -0.1 V vs. integrated Ag/AgCl reference electrode. The biosensor had a dynamic linear range of 10-400 µM, with a sensitivity of 9.04 µA mM-1 cm-2 and a low detection limit of 0.66 µM (S/N = 3). Additionally, the biosensor possesses strong anti-interference capability, high reproducibility, and storage stability over 3 weeks. Furthermore, its clinical applicability was tested in urine samples from both prostate cancer patients and healthy control, and the analytical recoveries were satisfactory. Therefore, this biosensor has significant potential in the rapid and non-invasive point-of-care testing for prostate cancer diagnosis.

Leaching behaviors and mechanisms of vitrified forms for the low-level radioactive solid wastes.

Leaching behaviors and mechanisms of commercialized glass wasteforms to sequester low-level solid-wastes were investigated: SG glass for resin waste and DG-2 glass for dry active waste. After ANS 16.1 leaching test, leachabilities of the nuclides, Co, Cs, and Sr, were all lager than 14, which met the requirement of the US-Nuclear Regulatory Commission. Holes of diameters 5-10 µm remained on the surface of the SG and crevices of lengths 10-50 µm were observed on the surface of the DG-2. We analyzed elemental compositions of the SG and the DG-2 with depths. For the SG, Si, Al, Ca, and Mg were accumulated and Na was depleted up to nearly 1.5 µm compared to an internal glass. For the DG-2, concentrations of B, Na, Al, Ca and Sr started to decrease from 2.5 µm even though other minor elements are still remained their concentrations. We suggested leaching mechanisms: alkali elements including H would diffuse through the holes on the SG, while most of the elements including Si and Al would diffuse through the crevices on the DG-2.

Water sensor for a nonaqueous solvent with poly(1,5-diaminonapthalene) nanofibers.

A water sensor for a nonaqueous solvent was fabricated using poly(1,5-diaminonapthalene (DAN) nanofibers, which were prepared through a catalytic chemical polymerization of the DAN monomer using Fe(III) salt as the catalyst. Poly(1,5-DAN) nanofibers were characterized by atomic force microscope (AFM), transmission electron microscope (TEM), scanning electron microscope (SEM), and UV-vis spectroscopy. The electrochemical properties of poly(1,5-DAN) nanofibers were investigated using cyclic voltammetry (CV). The electrochemical activity of poly(1,5-DAN) nanofibers was utilized for water sensing. The fabrication of water sensor was followed by placing one drop (about 2 microL) of 0.01% poly(1,5-DAN) nanofibers solution in the gap between two split gold electrodes (PBSA) and completely dried. The response of the water sensor in an acetonitrile solution was evaluated under optimized conditions. The linear dynamic range was from 0.05 to 20%, and the detection limit was determined to be 0.01%. The response of this sensor was shown to be comparable to that obtained with the Karl Fischer titration method.

A potentiometric non-enzymatic glucose sensor using a molecularly imprinted layer bonded on a conducting polymer.

A non-enzymatic potentiometric glucose sensor for the determination of glucose in the micomolar level in saliva was developed based on a molecularly imprinted polymer (MIP) binding on a conducting polymer layer. A MIP containing acrylamide, and aminophenyl boronic acid, as a host molecule to glucose, was immobilized on benzoic acid-functionalized poly(terthiophene) (pTBA) by the amide bond formation onto a gold nanoparticles deposited-screen printed carbon electrode (pTBA/AuNPs/SPCE). Aromatic boronic acid was incorporated into the MIP layer to stably capture glucose and create a potentiometric signal through the changed pKa value of polymer film by the formation of boronate anion-glucose complex with generation of H+ ions by the cis-diol reaction. Reversible binding and extraction of glucose on the sensor surface was observed using a quartz crystal microbalance. Each layer of the sensor probe was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The potentiometric response at the optimized conditions exhibited a wide linear dynamic range of 3.2×10-7 to 1.0×10-3M, with a detection limit of 1.9 (±0.15)×10-7M. The sensor probe revealed an excellent selectivity and sensitivity for glucose compared to other saccharides. In addition, the reliability of the proposed glucose sensor was evaluated in physiological fluid samples of saliva and finger prick blood.

Nitrogen ion implantation into various materials using 28 GHz electron cyclotron resonance ion source.

The installation of the 28 GHz electron cyclotron resonance ion source (ECRIS) ion implantation beamline was recently completed at the Korea Basic Science Institute. The apparatus contains a beam monitoring system and a sample holder for the ion implantation process. The new implantation system can function as a multipurpose tool since it can implant a variety of ions, ranging hydrogen to uranium, into different materials with precise control and with implantation areas as large as 1-10 mm(2). The implantation chamber was designed to measure the beam properties with a diagnostic system as well as to perform ion implantation with an in situ system including a mass spectrometer. This advanced implantation system can be employed in novel applications, including the production of a variety of new materials such as metals, polymers, and ceramics and the irradiation testing and fabrication of structural and functional materials to be used in future nuclear fusion reactors. In this investigation, the first nitrogen ion implantation experiments were conducted using the new system. The 28 GHz ECRIS implanted low-energy, multi-charged nitrogen ions into copper, zinc, and cobalt substrates, and the ion implantation depth profiles were obtained. SRIM 2013 code was used to calculate the profiles under identical conditions, and the experimental and simulation results are presented and compared in this report. The depths and ranges of the ion distributions in the experimental and simulation results agree closely and demonstrate that the new system will enable the treatment of various substrates for advanced materials research.

First results of 28 GHz superconducting electron cyclotron resonance ion source for KBSI accelerator.

The 28 GHz superconducting electron cyclotron resonance (ECR) ion source has been developed to produce a high current heavy ion for the linear accelerator at KBSI (Korea Basic Science Institute). The objective of this study is to generate fast neutrons with a proton target via a p(Li,n)Be reaction. The design and fabrication of the essential components of the ECR ion source, which include a superconducting magnet with a liquid helium re-condensed cryostat and a 10 kW high-power microwave, were completed. The waveguide components were connected with a plasma chamber including a gas supply system. The plasma chamber was inserted into the warm bore of the superconducting magnet. A high voltage system was also installed for the ion beam extraction. After the installation of the ECR ion source, we reported the results for ECR plasma ignition at ECRIS 2014 in Russia. Following plasma ignition, we successfully extracted multi-charged ions and obtained the first results in terms of ion beam spectra from various species. This was verified by a beam diagnostic system for a low energy beam transport system. In this article, we present the first results and report on the current status of the KBSI accelerator project.

Development of an ion beam analyzing system for the KBSI heavy-ion accelerator.

The Korea Basic Science Institute (KBSI) has been developing a heavy ion accelerator system to accelerate high current, multi-charge state ions produced by a 28 GHz superconducting electron cyclotron ion source. A beam analyzing system as a part of the low energy beam transport apparatus was developed to select charged particles with desirable charge states from the ion beams. The desired species of ion, which is generated and extracted from the ECR ion source including various ion particles, can be selected by 90° dipole electromagnet. Due to the non-symmetrical structure in the coil as well as the non-linear permeability of the yoke material coil, a three dimensional analysis was carried out to confirm the design parameters. In this paper, we present the experimental results obtained as result of an analysis of KBSI accelerator. The effectiveness of beam selection was confirmed during the test of the analyzing system by injecting an ion beam from an ECR ion source.

Ultrasensitive cytosensing based on an aptamer modified nanobiosensor with a bioconjugate: Detection of human non-small-cell lung cancer cells.

A novel aptamer-based amperometric nanobiosensor was designed for the sensitive and selective detection of A549 human non-small-cell lung cancer (NSCLC) cells. The cytosensing was performed using a MUC1 aptamer probe with a bioconjugate, where the probe was fabricated by the covalent immobilization on a conducting polymer nanocomposite formed through the self-assembly of 4-([2,2':5',2''-terthiophen]-3'-yl) benzoic acid (TTBA) on AuNPs. A bioconjugate composed of hydrazine and aptamer attached on AuNPs was used to reveal the selectively amplified detection signal. The cells were quantitatively analyzed using chronoamperometric measurements, and the results were further compared and confirmed using microscopic and DPV methods based on silver staining cytosensing experiments. The proposed aptasensor showed a high affinity for MUC1 positive lung cancer cells (A549) compared with the other control cancer cells, including human prostate (PC3), MUC1 negative normal lung (MRC-5), and liver tumors (HepG2) cells. An excellent dynamic range of the proposed method was obtained from 15 to 1×10(6) cells/mL with a detection limit of 8 cells/mL.

Towards vaporized molecular discrimination: a quartz crystal microbalance (QCM) sensor system using cobalt-containing mesoporous graphitic carbon.

A recent study on nanoporous carbon based materials (J. Am. Chem. Soc. 2012, 134, 2864) showed that the presence of abundant graphitized sp(2) carbon species in the frameworks led to higher affinity for aromatic hydrocarbons than their aliphatic analogues. Herein, improved understanding of the sensitive and selective detection of aromatic substances by using mesoporous carbon (MPC)-based materials, combined with a quartz crystal microbalance (QCM) sensor system, was obtained. MPCs were synthesized by direct carbonization of mesoporous polymers prepared from resol through a soft templating approach with Pluronic F127. The carbon-based frameworks can be graphitized through the addition of a cobalt source to the precursor solution, according to the catalytic activity of the cobalt nanoparticles formed during the carbonization process. From the Raman data, the degree of the graphitization was clearly increased by increasing the cobalt content and elevating the carbonization temperature. From a QCM study, it was proved that the highly graphitized MPCs exhibited a higher affinity for aromatic hydrocarbons than their aliphatic analogues. By increasing the degree of graphitization in the carbon-based pore walls, the MPCs showed both larger adsorption uptake and faster sensor response towards toxic benzene and toluene vapors.

Recondensation performance of liquid helium cryostat for a 28 GHz electron cyclotron resonance ion source.

Cryostat performance is essential for the stable operation of a superconducting magnet. A closed-cycle liquid helium cryostat was adopted for use for a superconducting electron cyclotron resonance (ECR) ion source by recondensing liquid helium vapor. The goal was to maintain the liquid helium filled reservoir at a constant level without transferring any liquid helium during the normal operation of the ECR ion source. To accomplish this, Gifford-McMahon (GM) refrigerators, which have two cold heads, were installed on the top of the cryostat. The cooling power of the GM cryocooler is 1.5 W at the second stage and 50 W at the first stage. Each stage was connected to the liquid helium reservoir, a radiation shield including high-Tc current lead, and related items. Before commissioning the ECR ion source, a preliminary evaluation of the recondensation performance was carried out with the magnet in partial operation. The design of the cryostat, its fabrication, and the experimental results are reported.

A simulation of X-ray shielding for a superconducting electron cyclotron resonance ion source.

It is generally assumed that large amounts of x-rays are emitted from the ion source of an Electron Cyclotron Resonance (ECR) instrument. The total amount of x-rays should be strictly limited to avoid the extra heat load to the cryostat of the superconducting ECR ion source, since they are partly absorbed by the cold mass into the cryostat. A simulation of x-ray shielding was carried out to determine the effective thickness of the x-ray shield needed via the use of Geant4. X-ray spectra of the 10 GHz Nanogan ECR ion source were measured as a function of the thickness variation in the x-ray shield. The experimental results were compared with Geant4 results to verify the effectiveness of the x-ray shield. Based on the validity in the case of the 10 GHz ECR ion source, the x-ray shielding results are presented by assuming the spectral temperature of the 28 GHz ECR ion source.

Superconducting magnet performance for 28 GHz electron cyclotron resonance ion source developed at the Korea Basic Science Institute.

A superconducting magnet for use in an electron cyclotron resonance ion source was developed at the Korea Basic Science Institute. The superconducting magnet is comprised of three solenoids and a hexapole magnet. According to the design value, the solenoid magnets can generate a mirror field, resulting in axial magnetic fields of 3.6 T at the injection area and 2.2 T at the extraction region. A radial field strength of 2.1 T can also be achieved by hexapole magnet on the plasma chamber wall. NbTi superconducting wire was used in the winding process following appropriate techniques for magnet structure. The final assembly of the each magnet involved it being vertically inserted into the cryostat to cool down the temperature using liquid helium. The performance of each solenoid and hexapole magnet was separately verified experimentally. The construction of the superconducting coil, the entire magnet assembly for performance testing and experimental results are reported herein.