Compared with the traditional Haber Bosch process, green and pollution-free electrocatalytic nitrogen reduction (NRR) has received considerable attention in the electrocatalysis field in the last decade. To address the issue of its low reactivity as well as the existence of competitive reactions, efficient electrocatalysts are particularly important. In this paper, NiO nanomaterials were synthesized by a simple water bath reaction. The effect of different calcination temperatures on the structure of NiO catalyst and its catalytic activity was studied. Uniform NiO-600 nanoparticles (56 ± 9.3 nm) obtained at 600 ℃ showed the best electrocatalytic NRR activity with an NH3 yield of 12 μg h− 1 mg− 1 and a Faraday efficiency of 5.5% at -0.5V (vs.RHE). The small particle size of the nanoparticles provided more active sites and the oxygen-rich vacancies facilitated the adsorption and activation of N2, which improved the catalytic activity of NiO-600. This study highlights the need for calcination temperature regulation and the huge impact on catalyst structure.
To investigate the effect of the catalyst and metal–support interaction on the methane decomposition behavior and physical properties of the produced carbon, catalytic decomposition of methane (CDM) was studied using Ni/SiO2 catalysts with different metal–support interactions (synthesized based on the presence or absence of urea). During catalyst synthesis, the addition of urea led to uniform and stable precipitation of the Ni metal precursor on the SiO2 support to produce Ni-phyllosilicates that enhanced the metal–support interaction. The resulting catalyst upon reduction showed the formation of uniform Ni0 particles (< 10 nm) that were smaller than those of a catalyst prepared using a conventional impregnation method (~ 80 nm). The growth mechanisms of methane-decomposition-derived carbon nanotubes was base growth or tip growth according to the metal–support interaction of the catalysts synthesized with and without urea, respectively. As a result, the catalyst with Ni-phyllosilicates resulting from the addition of urea induced highly dispersed and strongly interacting Ni0 active sites and produced carbon nanotubes with a small and uniform diameter via the base-growth mechanism. Considering the results, such a Ni-phyllosilicate-based catalyst are expected to be suitable for industrial base grown carbon nanotube production and application since as-synthesized carbon nanotubes can be easily harvested and the catalyst can be regenerated without being consumed during carbon nanotube extraction process.
High-temperature oxidation of a Ni-based superalloy was analyzed with samples taken from gas turbine blades, where the samples were heat-treated and thermally exposed. The effect of Cr/Ti/Al elements in the alloy on high temperature oxidation was investigated using an optical microscope, SEM/EDS, and TEM. A high-Cr/high-Ti oxide layer was formed on the blade surface under the heat-treated state considered to be the initial stage of high-temperature oxidation. In addition, a PFZ (γ’ precipitate free zone) accompanied by Cr carbide of Cr23C6 and high Cr-Co phase as a kind of TCP precipitation was formed under the surface layer. Pits of several μm depth containing high-Al content oxide was observed at the boundary between the oxide layer and PFZ. However, high temperature oxidation formed on the thermally exposed blade surface consisted of the following steps: ① Ti-oxide formation in the center of the oxide layer, ② Cr-oxide formation surrounding the inner oxide layer, and ③ Al-oxide formation in the pits directly under the Cr oxide layer. It is estimated that the Cr content of Ni-based superalloys improves the oxidation resistance of the alloy by forming dense oxide layer, but produced the σ or μ phase of TCP precipitation with the high-Cr component resulting in material brittleness.
Abstract In the present study, the effect of nickel nitrate addition as a catalytic precursor for the in situ formation of Ni nanoparticles during the heating process has been investigated on the modification of microstructure and graphitization of amorphous carbon resulting from pyrolysis of phenolic resin. For this purpose, the prepared resin samples were cured in carbon substrate with and without additives at temperatures of 800, 1000, and 1250 °C. XRD, FESEM, and TEM studies were performed to investigate the phase and microstructural changes in the samples during the heating process. In addition to phase and microstructural studies, thermodynamic calculations of the reactions performed for the in situ formation of nickel nanoparticles and their effective factors during the curing process were performed. The results indicated that nickel nitrate is transformed to nickel nanoparticles of different sizes during the reduction process in a reduced atmosphere. The in situ formation of nickel nanoparticles and its catalytic effect led to the graphitization of carbon resulting from the pyrolysis of phenolic resin at a temperature of 800 °C and above. By increasing temperature, the morphology of the formed graphite changed and hollow carbon nanotubes, carbon cells, and onion skin carbon were formed in the microstructure. It was also observed that by increasing the temperature and the amount of additive, carbon nanotubes and their size are increased. A noteworthy point from thermodynamic calculations during the formation of nickel nanoparticles was that the nickel nanoparticles themselves acted as accelerators of nickel oxide reduction reactions and the formation of nickel nanoparticles. This increases the amount of amorphous carbon graphitization resulting from the pyrolysis of phenolic resin which leads to the formation of more carbon nanotubes at higher temperatures.
In this paper, the effect of Ni (0, 0.5 and 1.0 wt%) additions on the microstructure, mechanical properties and electrical conductivity of cast and extruded Al-MM-Sb alloy is studied using field emission scanning electron microscopy, and a universal tensile testing machine. Molten aluminum alloy is maintained at 750 oC and then poured into a mold at 200 oC. Aluminum alloys are hot-extruded into a rod that is 12 mm in diameter with a reduction ratio of 39:1 at 550 oC. The addition of Ni results in the formation of Al11RE3, AlSb and Al3Ni intermetallic compounds; the area fraction of these intermetallic compounds increases with increasing Ni contents. As the amount of Ni increases, the average grain sizes of the extruded Al alloy decrease to 1359, 536, and 153 μm, and the high-angle grain boundary fractions increase to 8, 20, and 34 %. As the Ni content increases from 0 to 1.0 wt%, the electrical conductivity is not significantly different, with values from 57.4 to 57.1 % IACS.
본 연구는 51년 장기(1967-2017년) 수온 관측자료와 ONI(Oceanic Niño Index)를 이용하여 El Niño와 La Niña가 한국 동해 연안용승 발생에 미치는 영향을 파악하였다. 수온의 시계열분석 결과 하계 연안용승 발생빈도가 동해남부(울기~감포) 연안에서 가장 높았다. 하계 ONI 가 2.5 이상 급감하는 연변동이 발생한 1987-1988년과 1997-1998년에 동해 전 연안역(부산~고성)의 수온이 4~7 ℃ 급상승하였다. ONI가 1.5 이상으로 El Niño가 강한 1987, 1997년과 ONI가 –0.8 이하로 La Niña가 강한 1988, 1998년 동해 연안역의 수온구조가 서로 다르게 나타 났다. El Niño가 강한 시기 연안해역의 이상 수온은 음의 값으로 비교적 차가운 냉수괴가 분포한다. 이는 수온 경계층경사(Baroclinic tilting) 가 강해 연안역의 수온 성층 형성 수심이 얕아지기 때문이다. La Niña가 강한 시기는 El Niño가 강한 시기와 반대로 이상 수온은 양의 값으 로 수온이 높게 나타났다. 또한 수온의 경계층경사가 El Niño가 강한 시기에 비해 약해 수온 성층이 El Niño가 강한 시기보다 깊은 곳에 형 성된다. El Niño가 강한 시기 얕은 수심에 수온성층이 형성되는 현상은 하계 남풍계열의 바람에 의한 연안용승이 발생할 확률을 높일 수 있다. 반대로 La Niña가 강한 시기에는 남풍계열의 바람이 지속적으로 불어도 연안용승이 발생할 확률이 작다. 왜냐하면, 수온성층이 El Niño가 강한 시기에 비해 깊은 수심에서 형성되기 때문이다.
The effect of intercritical annealing temperature on the microstructure and mechanical properties of Fe-9Mn-0.2C- 3Al-0.5Si medium manganese steels containing Cu and Ni is investigated in this study. Six kinds of medium manganese steels are fabricated by varying the chemical composition and intercritical annealing temperature. Hardness and tensile tests are performed to examine the correlation of microstructure and mechanical properties for the intercritical annealed medium manganese steels containing Cu and Ni. The microstructures of all the steels are composed mostly of lath ferrite, reverted austenite and cementite, regardless of annealing temperature. The room-temperature tensile test results show that the yield and tensile strengths decrease with increasing intercritical annealing temperature due to higher volume fraction and larger thickness of reverted austenite. On the other hand, total and uniform elongations, and strain hardening exponent increase due to higher dislocation density because transformation-induced plasticity is promoted with increasing annealing temperature by reduction in reverted austenite stability.
In this study, the formation, microstructure, and wear properties of Colmonoy 88 (Ni-17W-15Cr-3B-4Si wt.%) + Stellite 1 (Co-32Cr-17W wt.%) coating layers fabricated by high-velocity oxygen fuel (HVOF) spraying are investigated. Colmonoy 88 and Stellite 1 powders were mixed at a ratio of 1:0 and 5:5 vol.%. HVOF sprayed selffluxing composite coating layers were fabricated using the mixed powder feedstocks. The microstructures and wear properties of the composite coating layers are controlled via a high-frequency heat treatment. The two coating layers are composed of γ-Ni, Ni3B, W2B, and Cr23C6 phases. Co peaks are detected after the addition of Stellite 1 powder. Moreover, the WCrB2 hard phase is detected in all coating layers after the high-frequency heat treatment. Porosities were changed from 0.44% (Colmonoy 88) to 3.89% (Colmonoy 88 + ST#1) as the content of Stellite 1 powder increased. And porosity is denoted as 0.3% or less by inducing high-frequency heat treatment. The wear results confirm that the wear property significantly improves after the high-frequency heat treatment, because of the presence of wellcontrolled defects in the coating layers. The wear surfaces of the coated layers are observed and a wear mechanism for the Ni-based self-fluxing composite coating layers is proposed.
We report the structural, morphological and magnetic properties of the Ni70Mn30 alloy prepared by Planetary Ball Mill method. Keeping the milling time constant for 30 h, the effect of different ball milling speeds on the synthesis and magnetic properties of the samples was thoroughly investigated. A remarkable variation in the morphology and average particle size was observed with the increase in milling speed. For the samples ball milled at 200 and 300 rpm, the average particle size and hence magnetization were decreased due to the increased lattice strain, distortion and surface effects which became prominent due to the increase in the thickness of the outer magnetically dead layer. For the samples ball milled at 400, 500 and 600 rpm however, the average particle size and hence magnetization were increased. This increased magnetization was attributed to the reduced surface area to volume ratio that ultimately led to the enhanced ferromagnetic interactions. The maximum saturation magnetization (75 emu/g at 1 T applied field) observed for the sample ball milled at 600 rpm and the low value of coercivity makes this material useful as soft magnetic material.
This study investigates the directional recrystallization behavior of Ni based oxide dispersion strengthened (ODS) alloy according to the zone annealing velocity. The zone annealing temperature is set as 1390oC, while the zone velocities are set as 2.5, 4, 6, and 10 cm/h, respectively. The initial microstructure observation of the as-extruded sample shows equiaxed grains of random orientation, with an average grain size of 530 nm. On the other hand, the zone annealed samples show a large deviation in grain size depending on the zone velocities. In particular, grains with a size of several millimeters are observed at 2.5-cm/h zone velocity. It is also found that the preferred orientation varies with the zone annealing velocity. On the basis of these results, this study discusses the role of zone velocities in the directional recrystallization of Ni base ODS alloy.
Porous graphites were synthesized by removing the template in HF after cabothermal conversion for 3 h at 900 ℃, accompanied by intercalations of pyrolyzed fuel oil (PFO) in the interlayer of Co or Ni loaded magadiite. The X-ray powder diffraction pattern of the porous graphites exhibited 00l reflections corresponding to a basal spacing of 0.7 nm. The particle morphology of the porous graphites was composed of carbon plates intergrown to form spherical nodules resembling rosettes like a magadiite template. TEM shows that the cross section of the porous graphites is composed of layers with very regular spaces. In particular, crystallization of the porous graphite was dependent on the content of Co or Ni loaded in the interlayer. The porous graphite had a surface area of 328-477 m2/g. This indicates that metals such as Co and Ni act as catalysts that accelerate graphite formation.
The influence of NiCrAlY bond coating on the adhesion properties of an Fe thermal coating sprayed on an Al substrate was investigated. By applying a bond coat, an adhesion strength of 21MPa was obtained, which was higher than the 15.5MPa strength of the coating without the bond coat. Formation of cracks at the interface of the bond coat and the Al substrate was suppressed by applying the bond coat. Microstructural analysis of the coating interface using EBSD and TEM indicated that the dominant bonding mechanism was mechanical interlocking. Mechanical interlocking without crack defects in the coating interface may improve the adhesion strength of the coating. In conclusion, the use of an NiCrAlY bond coat is an effective method of improving the adhesion properties of thermal sprayed Fe coatings on Al substrates.
The fatigue strength of a nickel-base superalloy was studied. Stress-controlled fatigue tests were carried out at 700 oC and 5 Hz using triangular wave forms. In this study, two kinds of testing procedures were adopted. One is the conventional tension-zero fatigue test(R = 0). The other was a procedure in which the maximum stress was held at 1000 MPa and the minimum stress was diverse from zero to 1000 MPa at 24 and 700 oC. The results of the fatigue tests at 700 oC indicate that the fracture mechanism changed according to both the mean stress and the stress range. At a higher stress range, γ ' precipitates are sheared by a/2<110> dislocation pairs coupled by APB. Therefore, in a large stress range, the deformation occurred by shearing of γ ' by a/2<110> dislocations, which brought about crystallographic shear fracture. As the stress range was decreased, the fracture mode gradually changed from crystallographic shear fracture to gradual growth of fatigue cracks. At an intermediate stress range, as it became more difficult for a/2<110> dislocation pairs to shear γ ' particles, cracks started to propagate in the matrix, avoiding the harder γ ' particles. High mean stress induced creep deformation, that is, γ ' particles were sheared by {111}<112> slip systems, which led to the formation of stacking faults in the precipitates. Thus, the change in fracture mechanism brought about the inversion of the S-N curves.
The effect of sublimable vehicle composition in the camphor-naphthalene system on the pore structure ofporous Cu-Ni alloy is investigated. The CuO-NiO mixed slurries with hypoeutectic, eutectic and hypereutectic compo-sitions are frozen into a mold at -25oC. Pores are generated by sublimation of the vehicles at room temperature. Afterhydrogen reduction at 300oC and sintering at 850oC for 1 h, the green body of CuO-NiO is completely converted toporous Cu-Ni alloy with various pore structures. The sintered samples show large pores which are aligned parallel to thesublimable vehicle growth direction. The pore size and porosity decrease with increase in powder content due to thedegree of powder rearrangement in slurry. In the hypoeutectic composition slurry, small pores with dendritic morphologyare observed in the sintered Cu-Ni, whereas the specimen of hypereutectic composition shows pore structure of plateshape. The change of pore structure is explained by growth behavior of primary camphor and naphthalene crystals dur-ing solidification of camphor-naphthalene alloys.
The aim of this paper is to consider the effect of annealing on the coefficient of thermal expansion (CTE) of electroplated Invar Fe-Ni alloy. The CTE of the as-electroplated alloy is lower than those of alloys annealed at 400˚C and 800˚C. XRD peaks become sharper as the as-electroplated alloy is annealed, which means the grain growth. The average grain sizes of as-electroplated and as-annealed alloys at 400˚C and 800˚C are 10 nm, 70 nm, and 2μm, respectively, as determined by TEM and EBSD analyses. The CTE variation for the various grain sizes after annealing may come from the magnetostriction effect, which generates strain due to changes in the magnetization state of the alloys. The thermal expansion coefficient is considered to be affected by nano grain size in electroplated Fe-Ni Invar alloys. As grain size decreases, ferromagnetic forces might change to paramagnetic forces. The effect of lattice vibration damping of nano grain boundaries could lead to the decrease of CTE.
In this study, we investigated the precipitation behavior of the R-phase precipitated at the initial stage of aging and its effects on the mechanical properties of 25%Cr-7%Ni-2%Mo-4%W super duplex stainless steel. The R-phase was mainly precipitated at the interface of ferrite/austenite phases and inside of the ferrite phase during the initial stage of aging. It was transformed into the σ-phase with an increase of the aging time. The ferrite phase was decomposed into a new austenite(γ2)phase and the σ-phase by an aging treatment. The R phase was an intermetallic compound showing higher molybdenum and tungsten concentrations than the matrix and also showed higher molybdenum and tungsten concentrations than the σ phase. In the initial stage of aging, precipitation of the R-phase did not change the hardness, the strength and the elongation. The hardness and the strength increased upon a longer aging time, but the elongation rapidly decreased. These results show that the R-phase did not significantly affect the hardness and the strength, though it did influence the elongation.
The effect of interstitial elements on the ductile-brittle transition behavior of austenitic Fe-18Cr-10Mn-2Ni alloys with different nitrogen and carbon contents was investigated in this study. All the alloys exhibited ductile-brittle transition behavior because of unusual low-temperature brittle fracture, even though they have a faced-centered cubic structure. With the same interstitial content, the combined addition of nitrogen and carbon, compared to the sole addition of nitrogen, improved the low-temperature toughness and thus decreased the ductile-brittle transition temperature (DBTT) because this combined addition effectively enhances the metallic component of the interatomic bonds and is accompanied by good plasticity and toughness due to the increased free electron concentration. The increase in carbon content or of the carbon-to-nitrogen ratio, however, could increase the DBTT since either of these causes the occurrence of intergranular fracture that lead to the deterioration of the toughness at low temperatures. The secondary ion mass spectroscopy analysis results for the observation of carbon and nitrogen distributions confirms that the carbon and nitrogen atoms were significantly segregated to the austenite grain boundaries and then caused grain boundary embrittlement. In order to successfully develop austenitic Fe-Cr-Mn alloys for low-temperature application, therefore, more systematic study is required to determine the optimum content and ratio of carbon and nitrogen in terms of free electron concentration and grain boundary embrittlement.
The effects of B4C on the mechanical properties of WC/Ni-Si hardmetal were analyzed using sintered bod- ies comprising WC(70-x wt.%), Ni (28.5 wt.%), Si (1.5 wt.%), and B4C (x wt.%), where 0 x 1.2 wt.%. Samples were prepared by a combination of mechanical milling and liquid-phase sintering. Phase and microstructure character- izations were conducted using X-ray diffractometry, scanning electron microscopy, and electron probe X-ray micro anal- ysis. The mechanical properties of the sintered bodies were evaluated by measuring their hardness and transverse rupture strength. The addition of B4C improved the sinterability of the hardmetals. With increasing B4C content, their hardness increased, but their transverse rupture strength decreased. The changes of sinterability and mechanical properties were attributed to the alloying reaction between B4C and the binder metal (Ni, Si). ≤ ≤
Ti-Ni alloys are widely used in numerous biomedical applications (e.g., orthodontics, cardiovascular science, orthopaedics) due to their distinctive thermomechanical and mechanical properties, such as the shape memory effect, superelasticity and low elastic modulus. In order to increase the biocompatibility of Ti-Ni alloys, many surface modification techniques, such as the sol-gel technique, plasma immersion ion implantation (PIII), laser surface melting, plasma spraying, and chemical vapor deposition, have been employed. In this study, a Ti-49.5Ni (at%) alloy was electrochemically etched in 1M H2SO4+ X (1.5, 2.0, 2.5) wt% HF electrolytes to modify the surface morphology. The morphology, element distribution, crystal structure, roughness and energy of the surface were investigated by scanning electron microscopy (SEM), energy-dispersive Xray spectrometry (EDS), X-ray diffractometry (XRD), atomic force microscopy (AFM) and contact angle analysis. Micro-sized pores were formed on the Ti-49.5Ni (at%) alloy surface by electrochemical etching with 1M H2SO4+ X (1.5, 2.0, 2.5) wt% HF. The volume fractions of the pores were increased by increasing the concentration of the HF electrolytes. Depending on the HF concentration, different pore sizes, heights, surface roughness levels, and surface energy levels were obtained. To investigate the osteoblast adhesion of the electrochemically etched Ti-49.5Ni (at%) alloy, a MTT test was performed. The degree of osteoblast adhesion was increased at a high concentration of HF-treated surface structures.