Target Material Research Articles

Effects of pulse time offset between Cr and Zr dual cathodes in closed-magnetic-field unipolar high-power impulse magnetron sputtering

Two cathode (target) materials, Cr and Zr, were paired in a closed-field magnetron dual-cathode configuration and used in unipolar high-power impulse magnetron sputtering (HiPIMS). Two pulse widths (pulse-on durations) and various pulse-time offsets between the negative-voltage pulses of the Cr and Zr targets were investigated by setting the synchronization delay between the HiPIMS power supplies of the two targets at two different Ar pressures. Several trends were observed by analyzing the waveforms of the target discharge current, target discharge voltage, and substrate current. The closed-magnetic-field dual-cathode configuration significantly enhanced the HiPIMS discharge efficiency of the Zr target at all pressures; however, the enhancement for the Cr target was considerably lower. The ion fluxes toward the substrate were influenced by two competing mechanisms. The charged species generated from the previous pulse on one target could be attracted by the subsequent pulse of the adjacent target as a preionized medium to enhance the HiPIMS discharge. However, the fraction of the previously emitted ion flux toward the substrate could be reduced. When a shorter pulse width of 70 μs was applied, the ion flux that reached the substrate was mainly affected by the pulse power of the Zr target, and delaying the pulses of the Cr target with a relatively lower ion yield can achieve a higher ion flux toward the substrate. Increasing the pulse width significantly increased ion fluxes emitted from both the Cr and Zr targets, increasing the total ion flux toward the substrate. The study indicates that for the Cr and Zr dual cathode pair, a pulse time offset of one pulse width plus more than approximately 200 μs would be the most efficient way to obtain the highest ion fluxes toward the substrate and achieve a better film quality.

Analysis of the accumulation of β-emitting radionuclides in the production of radiopharmaceuticals based on <sup>18</sup>F using the IBA CYCLONE 18/9 HC cyclotron

In order to clarify the scheme of radioactive waste management, the accumulation of undesirable beta-emitting radionuclides (PH) in the production of radiopharmaceuticals based on 18F using the IBA CYCLONE 18/9 HC cyclotron was investigated. It is shown that the dominant impurity PH is tritium, which is formed by the reaction of 18O(p, t) 16O when water is irradiated with [18O]H2O protons. The main proportion of 3H (about 95%) remains in the regenerated water. 1.6 % of the accumulated tritium activity is carried away from the synthesis zone with gases and water vapor. Tritium-containing waste (regenerated water in vials) can be considered as waste of a very low level of activity during disposal. With an increase in the operating time of the target over 2500 µA · h, the processes of corrosion /erosion of target materials increase, which leads to a sharp increase in the concentration of undesirable radionuclides in regenerated water, sorption purification cartridges and the finished dosage form. The concentration of tritium does not increase significantly. In the β-spectra of regenerated water [18O]H2O and the finished radiopharmaceutical [18F]NaF, in addition to the maximum due to tritium, a number of maxima appear in both the low- and high-energy parts of the spectrum. Other undesirable β-emitters accumulate in water as a result of leaching of the activated target wall. The possibility of using measurements of tritium activity in water [18O]H2O as an indicator of its re-enrichment has been demonstrated. The necessity of controlling the content of impurity beta-emitting PH in intermediate products, production waste and final radiopharmaceutical is shown.

Improved oxidation resistance of AIP NiCrAlYSi coatings by applying positive bias

The NiCrAlYSi coatings with a bias voltage of −30 V (N-coating) and + 5 V (P-coating) applied on the DD6 superalloy substrate were prepared by arc ion plating (AIP). The microstructure evolution and the oxidation resistance at 1100 °C of the two coatings were investigated. The results show that the positive bias could maintain the Al content from the target material through to the coating by enhancing droplet deposition proportion and resulting in better oxidation resistance. The as-deposited P-coating consists of γ-Ni, γ’-Ni3Al and α-Cr phases with significantly lower pores and ~ 1.1 wt% higher Al content than N-coating. The larger size (1.5 to 3.5 μm) block β-NiAl grains formed within P-coating after annealing at 1050 °C for 2 h, while it was not found in the N-coating. The oxidation parabolic rate constant at 1100 °C of annealed P-coating was confirmed as 3.54 × 10−3 mg2/(cm4·h), ~ 27.6 % lower than N-coating.

Quantifying the regime of thermodynamic control for solid-state reactions during ternary metal oxide synthesis.

The success of solid-state synthesis often hinges on the first intermediate phase that forms, which determines the remaining driving force to produce the desired target material. Recent work suggests that when reaction energies are large, thermodynamics primarily dictates the initial product formed, regardless of reactant stoichiometry. Here, we validate this principle and quantify its constraints by performing in situ characterization on 37 pairs of reactants. These experiments reveal a threshold for thermodynamic control in solid-state reactions, whereby initial product formation can be predicted when its driving force exceeds that of all other competing phases by ≥60 milli-electron volt per atom. In contrast, when multiple phases have a comparable driving force to form, the initial product is more often determined by kinetic factors. Analysis of the Materials Project data shows that 15% of possible reactions fall within the regime of thermodynamic control, highlighting the opportunity to predict synthesis pathways from first principles.

A Methodology for Shielding-Gas Selection in Wire Arc Additive Manufacturing with Stainless Steel.

The main objective of this work was to propose and evaluate a methodology for shielding-gas selection in additive manufacturing assisted by wire arc additive manufacturing (WAAM) with an austenitic stainless steel as feedstock. To validate the proposed methodology, the impact of multi-component gases was valued using three different Ar-based blends recommended as shielding gas for GMA (gas metal arc) of the target material, using CMT (cold metal transfer) as the process version. This assessment considered features that potentially affect the building of the case study of thin walls, such as metal transfer regularity, deposition time, and geometrical and metallurgical characteristics. Different settings of wire-feed speeds were conceived to maintain a similar mean current (first constraint for comparison's sake) among the three gas blends. This approach implied different mean wire-feed speeds and simultaneously forced a change in the deposition speed to maintain the same amount of material deposited per unit of length (second comparison constraint). The composition of the gases affects the operational performance of the shielding gases. It was concluded that by following this methodology, shielding-gas selection decision-making is possible based on the perceived characteristics of the different commercial blends.

Tailored Cis-Trans Isomeric Metal-Covalent Organic Frameworks for Coordination Configuration-Dependent Electrochemiluminescence.

Precise manipulation of the coordination configuration within substances can modulate the band structure and catalytic properties of the target material. Metal-covalent organic frameworks (MCOFs), a crystal material amalgamating the benefits of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), can integrate a predetermined coordination environment into the frameworks for amplifying the catalytic effect. In this study, we delicately synthesize isomeric MCOFs using bis(glycinato)copper as the aminoligand via kinetically and thermodynamically favorable pathways to yield cis-MCOF and trans-MCOF products, respectively, thereby introducing a cis-trans isomeric coordination field into the framework. Moreover, the twisted skeleton derived from the flexibility of amino acid and β-ketoenamine linkages endows trans-MCOF with surprising water dispersibility. Compared to cis-MCOF, the trans isomerism displays a significant enhancement in cathodic electrochemiluminescence via the catalysis of Cu nodes toward K2S2O8. The density of states analysis shows that the d-band center of trans-MCOF is closer to the Fermi level, leading to more stable adsorption binding to promote the catalysis. This study is the first report on constructing predesign coordination configuration MCOFs via an easy-handling method, which gives the guidelines for the design of amino acid-based MCOF materials.

High repetition-rate dual-channel X-ray spectrometer for high-intensity laser-plasma experiments.

We describe the development and demonstration of a high-repetition-rate-capable dual-channel (DC) x-ray spectrometer designed for high-intensity laser-plasma experiments (≥1×1021 W/cm2). The spectrometer, which operates at high repetition rates, is limited only by the refresh rate of targets and the camera's frame rate. It features two channels, each equipped with a flat highly oriented pyrolytic graphite (HOPG) crystal and a unique detector plane, allowing it to resolve two distinct x-ray bands: approximately 7-10 and 10-13keV. Each detector plate carrier holds two slots for active (scintillators) or passive (imaging plates) x-ray detectors. We present the design and testing of the HR-DC-HOPG using both the COMET laser (10J, 0.5ps shot/4min) at LLNL's Jupiter Laser Facility and the SCARLET laser (10J, 30fs shot/min) at Ohio State University. The results demonstrate the spectrometer's performance across various laser energies, target materials, pulse shapes, and detector types.

Examination of the Odor-Eliminating Effect of a Deodorizing Spray on the Volatile Odorants of Malignant Wounds.

This study aimed to compare the odor components before and after spraying a deodorizing spray (DS) on volatile odorants in malignant wounds (MWs) in women with breast cancer; a secondary aim was to evaluate the deodorizing effect of the DS. This is an observational study. We investigated 3 patients who had MWs resulting from breast cancer. Participants were recruited from outpatient clinics in the Breast Surgery Department, University Hospital, Kanagawa, Japan. The target material was exudate-containing dressings collected from MWs. After collection, the odor components (air) were collected into a sampling bag by using a handheld pump. Then, after 5 sprays of a DS, air was collected in the same manner. All odor components were analyzed objectively by gas chromatography-mass spectrometry-olfactometry (GC/MS-O). The concentration in parts per million (ppm) of the main odor components in the air before and after spraying DS was compared, and the residual concentration rate (%) was calculated. Sniffing tests before and after spraying were also conducted to determine the subjective deodorizing effect of DS. Of the possible hundreds of volatile odorants, 3 to 11 main components of volatile odorants were detected per subject. After DS spraying, the odorants dimethyl disulfide, dimethyl trisulfide, and benzyl alcohol were reduced according to GC/MS-O. The residual concentration of the following main odor components was also reduced: benzyl alcohol (30%), octanal (56%), p-dichlorobenzene (56%), isovaleric acid (56%), propylene glycol (63%), and nonanal (66%). DS was effective against some volatile odorants in MWs, but no clear deodorizing effect was observed. Since there are individual differences in the type and number of odorants in MWs, the use of DS needs to be examined and verified in a larger number of cases.

Deformability, inherent mechanical properties and chemical bonding of Al11Nd3 in Al-Nd target material

Microstructure uniformity of the Al-Nd target materials with Al11Nd3 significantly affects the performance of the fabricated Al-Nd film, which is widely used as wiring material in large-size thin-film transistor liquid crystal display (TFT-LCD) panels. Understanding the inherent mechanical properties and chemical bonds of Al11Nd3 is crucial for homogenizing the Al-Nd target. Here, by a combined experimental and ab-initio theoretical study, the microstructure and deformability of the Al-3wt%Nd alloy and the inherent mechanical properties and chemical bonds of Al11Nd3 were investigated comprehensively. The Al-3wt%Nd alloy is composed of the pre-eutectic α-Al matrix and the eutectic α-Al and a high stable α-Al11Nd3 phase. During the plastic deformation, the eutectic microstructure transforms from a cellular to a lamellar shape, while the morphology and dimension of α-Al11Nd3 are not changed significantly. By examining ideal tensile strength, elastic moduli, hardness and brittleness-ductility, the hardness-brittleness of α-Al11Nd3 is quantitatively evaluated, accounting for its difficulties of plastic deformation and fragmentation. Combining band structure, population analysis, topological analysis and crystal orbital Hamilton population, we found that α-Al11Nd3 possesses two types of chemical bonds: the Nd-Al and Al-Al bonds. The former is a typical ionic bond with electron transfer from Nd to Al, while the latter, dominated by both 3s-3p and 3p-3p interactions, is a weak covalent bond. The mixed chemical bond is responsible for the high hardness-brittleness of α-Al11Nd3. This work is expected to lay a foundation for Al-Nd alloy and catalyze the fabrication of high-quality Al-Nd target materials.

Production of Dark Sector Particles via Resonant Positron Annihilation on Atomic Electrons.

Resonant positron annihilation on atomic electrons provides a powerful method to search for light new particles coupled to e^{+}e^{-}. Reliable estimates of production rates require a detailed characterization of electron momentum distributions. We describe a general method that harnesses the target material Compton profile to properly include electron velocity effects in resonant annihilation cross sections. We additionally find that high-Z atoms can efficiently act as particle physics accelerators, providing a density of relativistic electrons that allows one to extend by several times the experimental mass reach.

Surface modification of W–Ta–V–Cr multi-component alloy after low-energy He plasma irradiation

This study explores a hypothetical scenario where low-activation refractory multi-component alloys (RMCAs) are considered for use as divertor target materials in fusion reactors. To investigate the surface modifications under divertor service conditions, a multi-phase W–Ta–V–Cr RMCA is irradiated with low-energy helium (He) plasma at varying temperatures to approximately 5.0 × 1025 He·m−2. The W-rich and Cr-rich phases in the multi-phase RMCA mimic the mono-phase W–Ta–V–Cr RMCA and segregation at grain boundaries, respectively. Following irradiation, fuzz layer formation is observed for all phases at temperatures lower than pure W requires. Additionally, nano He bubbles are identified in the fuzz tendrils at 920 °C. The modified layers exhibit reduced V and Cr content with increasing temperature, transitioning into W-Ta binary alloys at 920 °C. Notably, the fuzz layer on the W-rich phase is thinner than that on pure W at 920 °C. While a thinner fuzz layer suggests the alloy’s potential as a divertor target material, challenges include a lower fuzz formation temperature and potential high V and Cr sputtering yield, raising concerns for plasma contamination during fusion reactor operation. This dual perspective highlights both the promise and challenges of utilizing RMCAs as divertor target materials in severe fusion reactor environments.

Production of High-Power Nitrogen Sputtering Plasma for TiN Film Preparation

High-density nitrogen plasma was produced using a high-power pulsed power modulator to sputter titanium targets for the preparation of titanium nitride film. The high-power pulsed sputtering discharge unit consisted of two targets facing each other with the same electrical potential. The titanium target plates were used as target materials with dimensions of 60 mm length, 20 mm height, and 5 mm thickness. The gap length was set to be 10 mm. The magnetic field was created with a permanent magnet array behind the targets. The magnetic field strength at the gap between the target plates was 70 mT. The electrons were trapped by the magnetic and electric fields to enhance the ionization in the gap. The nitrogen and argon gases were injected into the chamber with 4 Pa gas pressure. The applied voltage to the target plates had an amplitude from −600 V to −1000 V with 600 μs in pulse width. The target current was approximately 10 A with the consumed power of 13 kW. The discharge sustaining voltage was almost constant and independent of the applied voltage, in the same manner as the conventional normal glow discharge. The ion density and electron temperature at the surface of the ionization region were obtained as 1.7 × 1019 m−3 and 3.4 eV, respectively, by the double probe measurements. The vertical distribution of ion density and electron temperature ranged from 1.1 × 1017 m−3 (at 6 cm from the target edge) to 1.7 × 1019 m−3 and from 2.4 eV (at 6 cm from the target edge) to 3.4 eV, respectively. From the emission spectra, the intensities of titanium atoms (Ti I), titanium ions (Ti II), and nitrogen ions (N2+) increased with increasing input power. However, the intensities ratio of Ti II to Ti I was not affected by the intensities from N2+.

Effect of insulation materials and power on microwave heating characteristics of SiC susceptor under material–specific parametric conditions

High-quality microwave absorber materials play a crucial role in the efficient and uniform processing of variety of materials through microwave hybrid heating. Silicon carbide (SiC) is an excellent microwave absorber at room temperature, which enhances the heating rate of the target materials significantly. In the present study, effects of heat insulation materials and their configurations on microwave heating characteristics of SiC were investigated at different power levels. The responses were assessed in terms of the heating capability (maximum temperature achieved), radiation heat loss, temperature gradient, and heating uniformity under different parametric conditions. A 3D COMSOL Multiphysics simulation model, coupled with microwave heating and heat transfer module, was developed with surface-to-ambient radiation boundary conditions. Electromagnetic and thermal properties of the SiC utilized in the model were selected based on physical properties, such as porosity/density, particle size, and chemical composition of SiC. The model outputs were validated with experimental findings. Results showed that microwave heating characteristics were highly sensitive to the susceptor (SiC) properties, insulation materials and power levels. Insulation materials prevented heat losses significantly; at the same time, different insulation configurations altered the electrical field intensity distribution within the SiC sample, which affected the responses. Microwave power levels also influenced the responses and quantity of insulation required.

Preparation and Performance of a Cr/CrN/TiAlCN Composite Coating on a GCr15 Bearing Steel Surface

In order to enhance the surface properties of GCr15 bearing steel, a TiAlCN coating with a low friction coefficient, high hardness, and excellent adhesion was fabricated. The TiAlCN multilayer coating was deposited onto the GCr15 bearing steel surface using magnetron sputtering technology, and optimal coating parameters were achieved by adjusting the number of layers, sputtering power of the graphite target, and coating duration. The experimental results showed that adding Cr/CrN as a transition layer between GCr15 bearing steel and TiAlCN significantly improved multiple properties of the coating. Adding carbon atoms caused TiAlN to dissolve into a TiAlCN structure, enhancing multiple properties of the coating. With the increase in the sputtering power of the graphite target material, the hardness, friction, and wear performance of the coating showed a trend of first increasing and then decreasing. The hardness of the coating gradually increased with time, and the friction coefficient and wear amount first decreased and then increased. When the sputtering power of the graphite target material was 100 W and the coating time was 4800 s, the coating performance was optimal. The hardness was 876 HV, the friction coefficient was 0.42, the wear amount was 1 × 10−4 g, and the wear rate was 2.8 × 10−6 g/m·N under optimal process parameter conditions.

Efficient production and purification of 32P radioisotope from sulfur by dry distillation: A practical approach with high radiochemical purity

The 32P radioisotope, with a half-life of 14.3 days and an energy level of 1.71 MeV, has diverse applications in medicine and research. Consequently, producing a carrier-free 32P radioisotope characterized by high radiochemical and radionuclide purity is imperative. Two primary methods for generating 32P radioisotopes exist: irradiating phosphorus through the nuclear reaction (n,γ) or irradiating sulfur through the nuclear reaction (n,p). Using sulfur as a target material provides several advantages. Besides the fact that the chemical element produced after irradiation (32P) differs from the irradiated element (32S), it also produces a32P radioisotope with a higher specific activity than using 31P as the target. The production of the radioisotope 32P from sulfur employs the dry distillation method, capitalizing on sulfur's easily sublimated nature. The volatility of sulfur when heated makes it easy to separate the resulting sulfur and radioisotope 32P without the need for additional reagents. This research aims to establish a practical method for producing the 32P radioisotope using the dry distillation technique. The dry distillation method utilizes a quartz ampoule containing a mixture of 32P and 35S radionuclides, a distillation tube wrapped with heating tape, and a condenser to collect the distilled sulfur. Sulfur, serving as the target material, undergoes irradiation in the reactor at the Central Irradiation Position (CIP) through the 32S(n,p)32P nuclear reaction with a fast neutron flux of 5.380 × 1013 n/cm2.sec. Separation is achieved through distillation at a temperature of 440 °C. The residual separation products are then dissolved in a 0.1 N HCl solution. The purification process involves using an AG50 WX8 cation exchange resin column, which is pre-conditioned with 0.1 N HCl. The resulting eluate contains the 32P radioisotope. The radiochemical purity of the 32P radioisotope is analyzed using thin-layer chromatography (TLC). In this analysis, a PEI Cellulose plate serves as the stationary phase, and a KH2PO4 solution acts as the mobile phase. This vacuum-free distillation method successfully separates the 32P radioisotope from sulfur, achieving a separation efficiency of 55.1 ± 9.9% (n = 7). The average activity produced after the purification process is 5.690E+10 Bq. Purifying the 32P radioisotope results in a radiochemical purity of 99.97% at Rf 0.7110, as orthophosphate, the radionuclide purity exceeds 99%.

Comparative study of effect of fragment nose shapes on damage characteristics of thin target plate in ballistic applications

Experimental and numerical investigations in ballistic applications have predominantly focused on determining the ballistic limit of target plates for various projectile shapes. However, limited attention has been given to the influence of projectile nose shapes at high impact velocities. To address this gap, 3D FE simulations were carried out on a 1 mm thin target plate using J-C material model, the Gruneisen equation of state (EOS), an erosion contact algorithm, and the explicit FE code LS-DYNA. The simulations involved impact of fragments of equal mass but different nose shapes. The results revealed a significant influence of fragment shape on both the ballistic limit and overall plastic deformation of the target plate. Particularly, the target plate impacted by a hexagonal pyramid fragment shape exhibited the highest ballistic limit and global plastic deformation. Further, it was also observed that at higher impact velocities, the former fragment shape caused the maximum damage to the target plate, while at lower impact velocities, the cubical fragment shape demonstrated the highest lethality. This difference in target damage is known to be governed by the energy required to erode the target and fragment material. The results from the current study offers valuable insights into how different fragment shapes influence the damage inflicted on target plates in ballistic scenarios. The findings presented in this study also offer guidance on selecting suitable fragment shapes for future use in Fragment Generator Warheads (FGW) in order to maximize the damage or lethality inflicted on targets.

Separation of terbium as a first step towards high purity terbium-161 for medical applications.

Terbium-161 is a medical radiolanthanide that has a beta decay energy and half-life similar to that of lutetium-177, which makes it a promising alternative for therapeutic purposes. The production route using an enriched gadolinium-160 target necessitates the purification of terbium-161 from the untransmuted target material as well as from its stable decay product, dysprosium-161. The separation of neighbouring lanthanides is challenging due to their similar chemical properties and prominent trivalent oxidation states. In this work, the aim is to change the oxidation state of terbium, resulting in the altering of chemical properties that ease the intragroup separation. To this end, a novel separation method is investigated, involving the electrochemical oxidation of terbium (3+) to terbium (4+) followed by anion exchange chromatography. The electrolysis conditions are set to the highest achievable conversion rate, followed by a dilution step during which the pH and electrolyte concentration are slightly lowered to obtain conditions that are compatible with the separation method. XAS analysis is done to characterize the carbonato complex of both oxidation states and to further elucidate the separation mechanism. The results show that the separation approach of combining electrochemical oxidation with anion exchange chromatography is promising for the purification of 161Tb for medical use.

Effect of radiation defects on grain boundary evolution under shock loading

Grain boundary (GB) failure in tungsten under shock loading after irradiation is a key factor to estimate the performance of tungsten as a plasma facing material in nuclear fusion reactors and as a target in spallation neutron sources. In this work, GB evolution after absorption of different radiation defect clusters under shock loading has been investigated at atomic scale through non-equilibrium molecular dynamics (NEMD) method. Different to the cases without radiation defects, after absorption of interstitial dislocation loops and voids, two mechanisms have been identified for the decrease of critical shock velocity (vc) and the related GB failure. The direct void growth accompanied by appearance of disordered structure around void, from the remaining vacancy cluster which could not be annihilated by compressive stress wave, is the 1st mechanism. In the 2nd mechanism, activation of slip systems, dislocation formation, motion and multiplication, void nucleation and growth dominate the failure process. The higher potential energy and local stress concentration around a defect absorption region in GB are recognized for atomic motion deviations from shock loading direction, resulting in formation of disordered structure, activation of slip system and dislocation multiplication with lower vc under coupling effects of radiation damage and shock loading. These results indicate that under a high dose of radiation damage, GB failure induced by shock loading should be considered seriously in order to estimate the lifetime of tungsten-based plasma facing materials and spallation target materials.

Relationship between calcium forms and organic carbon content in aggregates of calcareous soils in northern China

The agricultural soil organic carbon (SOC) pool is one of the most active C pools in terrestrial ecosystems, and soil aggregates are the main site of SOC fixation. Mineral sorption plays a crucial role in SOC accumulation. Calcium (Ca) is a typical soil mineral element that plays a crucial role in SOC accumulation and is fundamental for the formation of soil aggregates. Although Ca has been shown to regulate the stability of SOC, the relationship between different forms of Ca and SOC within aggregates in northern China remains unclear. In this study, we selected five soils (black soil, light chernozem soil, fluvo-aquic soil, sierozem soil, and loess soil) with different calcium carbonate (CaCO3) contents as the target materials. Water-stable aggregates were separated using the wet-sieving method. Soil respiration was measured using the static alkali absorption method (carbon dioxide [CO2] absorption by NaOH solution). The CaCO3 content was quantified using the CO2 gas volume method, and the continuous leaching method was used to analyze the different forms of Ca (water soluble-Ca, exchangeable-Ca, acid soluble-Ca, and bound to organic-Ca). In-situ field sampling was used to reveal the associations between different forms of Ca and SOC within aggregates. The results showed that besides the CaCO3 form, exchangeable-Ca (20.06 %–57.86 %) and bound to organic-Ca (26.69 %–73.91 %) were major Ca forms in calcareous soils. There was a nonsignificant negative correlation between CaCO3, acid soluble-Ca, and exchangeable-Ca and SOC in the bulk soil. However, there was a significant negative correlation among CaCO3, acid soluble-Ca, and exchangeable-Ca with SOC in macro-aggregates (> 0.25 mm) and micro-aggregates (0.25–0.053 mm). A 90-day incubation experiment was conducted to verify the previous speculations, which revealed that CaCO3 increased SOC mineralization and reduced the content of SOC, while enhancing the acid soluble-Ca and bound to organic-Ca content. In the treatment with added CaCO3, there was a negative correlation between acid soluble-Ca and bound to organic-Ca and SOC in bulk soil and macro-aggregates (> 0.25 mm). The effect of Ca2+ on SOC should not be ignored. Excessive Ca2+ may be converted into different forms of Ca to occupy the bonding sites for SOC on the surface of soil particles with silt and clay particles, forming a pseudo-aggregate structure, and the SOC traveling between soil particles, which is not conducive to SOC stabilization and accumulation.

Designing core-shell heterostructure based on C–ZnSe–CoSe2/Zn–Co-ZIF derived from reconstructed ZIFs shelled with NiCo–OH nanosheets to enhance guanine electrocatalysis performance

This paper focuses on the fabrication of electrochemical sensor based on core–shell heterostructure of NiCo–OH@C–ZnSe–CoSe2/Zn–Co-ZIF to efficient recognition of guanine. First, the bimetallic Zn/Co-ZIF precursor was obtained via facile solvothermal method and then coated with uniform PDA layer. Finally, the target material named PDA@Zn/Co-ZIF was synthesized by selenization and calcination processes at inert atmosphere and used as a core. The combination of reconstructed ZIFs as a core and transition metal layered double hydroxides (LDHs) as a shell led to the construction of a new catalyst with a core-shell structure and unique properties such as more exposed electrochemical active sites and high conductivity due to the strong synergistic effects between core and shell. The guanine based amperometric sensor was shown two linear responses in the range of 0.1 μM–2 μM and 2 μM–56 μM with a detection limit of 0.03 μM (S/N = 3). In addition, the proposed sensor exhibited satisfactory reproducibility with relative standard deviation (RSD) of 1%, excellent anti-interference ability, and favorable stability.