Proceedings of the Korean Institute of Surface Engineering Conference
/
2001.11a
/
pp.29-30
/
2001
This paper presents some results of plasma nitriding on hard chromium deposit. The substrates were C45 steel and $30~50{\;}\mu\textrm{m}$ of chromium deposit by electroplating was formed. Plasma nitriding was carried out in a plasma nitriding system with $95NH_3{\;}+{\;}SCH_4$ atmosphere at the pressure about 600 Pa and different temperature from $450^{\circ}C{\;}to{\;}720^{\circ}C$ for various time. Optical microscopy and X-ray diffraction were used to evaluate the characteristics of surface nitride layer formed by nitrogen diffusion from plasma atmosphere inward iCr coating and interface carbide layer formed by carbon diffusion from substrate outward Cr coating. The microhardness was measured using microhareness tester at the load of 100 gf. Corrosion resistance was evaluated using the potentiodynamic measurement in 3.5% NaG solution. A saturated calomel electrode (SiCE) was used as the reference electrode. Fig.1 shows the typical microstructures of top surface and cross-section for nitrided and unnitrided samples. Aaer plasma nitriding a sandwich structure was formed consisting of surface nitride layer, center chromium layer and interface carbide layer. The thickness of nitride and carbide layers was increased with the increase of processing temperature and time. Hardness reached about 1000Hv after nitriding while 900Hv for unnitrided hard chromium deposit. X-ray diffraction indicated that surface nitrided layer was a mixture of $Cr_2N$ and CrN at low temperature and erN at high temperature (Fig.2). Anodic polarization curves showed that plasma nitriding can greatly improve the corrosion resistance of chromium e1ectrodeposit. After plasma nitriding, the corrosion potential moved to noble direction and passive current density was lower by 1 to 4 orders of magnitude compared with chromium deposit(Fig.3).
Young Chun Ko;Byung Ho Park;Hae Jin Kim;Q Won Choi;Jongbaik Ree;Keun Ho Chung
Bulletin of the Korean Chemical Society
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v.15
no.2
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pp.122-126
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1994
Corrosion of brass coated steel cords in the acetonitrile solution of sulfenamide derivatives, N-Cyclohexylbenzothiazole-2-sulfenamide (CBTS), N,N'-Dicyclohexylbenzothiazole-2-sulfenamide (DCBS), N-tert-Butylbenzothiazole-2-sulfenamide (TBBS), N-tert-Amylbenzothiazole-2-sulfenamide (TABS), and N-Oxydiethylbenzothiazole-2-sulfenamide (OBTS) was investigated by potentiostatic anodic and cathodic polarization (Tafel plot), DC polarization resistance, and AC impedance measurements. The corrosion current densities and rates are 1.236 ${\mu}A /cm^2$ and 0.655 MPY for CBTS; 1.881 ${\mu}A/cm^2$ and 0.988 MPY for DCBS; 2.367 ${\mu}A/cm^2$ and 1.257 MPY for TBBS; 3.398 ${\mu}A /cm^2$ and 1.809 MPY for TABS, respectively. OBTS among derivatives under study shows the lowest corrosion density (0.546 ${\mu}A /cm^2$) and the slowest corrosion rate (0.288 MPY). Also, the charge transfer resistances and the double layer capacitances are 275.21 $k{\Omega}{\cdot}cm^2$ and 7.0 ${\mu}F{cdot}cm^{-2}$ for CBTS; 14.24 ${\mu}F{\cdot}cm^2$ and 26 ${\mu}F{\cdot}cm^{-2}$ for DCBS; 54.15 $k{\Omega}{\cdot}cm^2$ and 26 ${\mu}F{\cdot}cm^{-2}$ for TBBS; 0.96$k{\Omega}{\cdot}cm^2$ and 83 ${\mu}F{\cdot}cm^{-2}$ for TABS, respectively. The weaker the electron donating inductive effect of derivatives is and the smaller the effect of steric hindrance is, the more the corrosion of brass coated steel cords in the acetonitrile solution of sulfenamide derivatives is prevented. The above results agree with that observed in the field of tire industry.
Active reaction sites and electrochemical O2 reduction kinetics on La_{1-x}Sr_xMnO_{3+{\delta}} (x=0.1-0.4)/YSZ (yttria-stabilized zirconia) electrodes are investigated in the temperature range of 700-900 ℃ at $Po_2=10^{-3}$-0.21 atm. Results of the steady-state polarization measurements, which are formulated into the Butler-Volmer formalism to extract transfer coefficient values, lead us to conclude that the two-electron charge transfer step to atomically adsorbed oxygen is rate-limiting. The same conclusion is drawn from the $Po_2$-dependent ac impedance measurements, where the exponent m in the relationship of $I_o$ (exchange current density) ∝ $P_{o_{2}}^m$ is analyzed. Chemical analysis is performed on the quenched Mn perovskites to estimate their oxygen stoichiometry factors (δ) at the operating temperature (700-900 ℃). Here, the observed δ turns out to become smaller as both the Sr-doping contents (x) and the measured temperature increase. A comparison between the 8 values and cathodic activity of Mn perovskites reveals that the cathodic transfer coefficients $({\alpha}_c)$ for oxygen reduction reaction are inversely proportional to δ whereas the anodic ones $({\alpha}_a)$ show the opposite trend, reflecting that the surface oxygen vacancies on Mn perovskites actively participate in the $O_2$ reduction reaction. Among the samples of x= 0.1-0.4, the manganite with x=0.4 exhibits the smallest 8 value (even negative), and consistently this electrode shows the highest ${\alpha}_c$ and the best cathodic activity for the oxygen reduction reaction.
Meneses, Fernando;Urreta, Silvia E.;Escrig, Juan;Bercoff, Paula G.
Current Applied Physics
/
v.18
no.11
/
pp.1240-1247
/
2018
Magnetic hysteresis in Ni nanowire arrays grown by electrodeposition inside the pores of anodic alumina templates is studied as a function of temperature in the range between 5 K and 300 K. Nanowires with different diameters, aspect ratios, inter-wire distance in the array and surface condition (smooth and rough) are synthesized. These microstructure parameters are linked to the different free magnetic energy contributions determining coercivity and the controlling magnetization reversal mechanisms. Coercivity increases with temperature in arrays of nanowires with rough surfaces and small diameters -33 nm and 65 nm- when measured without removing the alumina template and/or the Al substrate. For thicker wires -200 nm in diameter and relatively smooth surfaces- measured without the Al substrate, coercivity decreases as temperature rises. These temperature dependences of magnetic hysteresis are described in terms of an effective magnetic anisotropy $K_a$, resulting from the interplay of magnetocrystalline, magnetoelastic and shape anisotropies, together with the magnetostatic interaction energy density between nanowires in the array. The experimentally determined coercive fields are compared with results of micromagnetic calculations, performed considering the magnetization reversal mode acting in each studied array and microstructure parameters. A method is proposed to roughly estimate the value of $K_a$ experimentally, from the hysteresis loops measured at different temperatures. These measured values are in agreement with theoretical calculations. The observed temperature dependence of coercivity does not arise from an intrinsic property of pure Ni but from the nanowires surface roughness and the way the array is measured, with or without the alumina template and/or the aluminum support.
Cu based amorphous ($Cu_{54}Zr_{22}Ti_{18}Ni_{6}$) powders were deposited onto Al 6061 substrates by cold spray process with different powder preheating temperatures (below glass transition temperature: $350^{\circ}C$, near glass transition temperature: $430^{\circ}C$ and near crystallization temperature: $500^{\circ}C$). The microstructure and macroscopic properties (hardness, wear and corrosion) of Cu based amorphous coating layers were also investigated. X-ray diffraction results showed that cold sprayed Cu based amorphous coating layers of $300{\sim}350{\mu}m$ thickness could be well manufactured regardless of powder preheating temperature. Porosity measurements revealed that the coating layers of $430^{\circ}C$ and $500^{\circ}C$ preheating temperature conditions had lower porosity contents (0.88%, 0.93%) than that of the $350^{\circ}C$ preheating condition (4.87%). Hardness was measured as 374.8 Hv ($350^{\circ}C$), 436.3 Hv ($430^{\circ}C$) and 455.4 Hv ($500^{\circ}C$) for the Cu based amorphous coating layers, respectively. The results of the suga test for the wear resistance property also corresponded well to the hardness results. The critical anodic current density ($i_{c}$) according to powder preheating temperature conditions of $430^{\circ}C$, $500^{\circ}C$ was lower than that of the sample preheated at $350^{\circ}C$, respectively. The higher hardness, wear and corrosion resistances of the preheating conditions of near $T_{g}$ and $T_{x}$, compared to the properties of below $T_{g}$, could be well explained by the lower porosity of coating layer.
Journal of the Korea Academia-Industrial cooperation Society
/
v.10
no.12
/
pp.3731-3739
/
2009
One-chambered sediment cells with a variety of anodic electrodes were tested for generation of electricity. Material used for anodes was iron, brass, zinc/iron, copper and graphite felt which was used for a common cathode. The estuarine sediment served as supplier of oxidants or electron-producing microbial habitat which evoked electrons via fast metal corrosion reactions or a complicated microbial electron transfer mechanism, respectively. Maximum power density and current density were found to be $6.90\;W/m^2$ (iron/zinc) and $7.76\;A/m^2$ (iron), respectively. Interestingly, copper wrapped with carbon cloth produced better electric performance than copper only, by 60%, possibly because the cloth not only prevented rapid corrosion on the copper surface by some degrees, but also helped growing some electron-emitting microbes on its surface. At anodes oxidation reduction potential(ORP) was kept to be stationary over time except at the very initial period. The pH reduction in the copper and copper/carbon electrodes could be a sign of organic acid production due to a chemical change in the sediment. The simple estimation of interfacial, electrical resistances of electrodes and electrolyte in the sediment cell that a key to the electricity generation should be in how to control corrosion rate or microbial electron transfer activity.
The peculiar feature of cathodic protection in seawater has the capability to form mineral calcareous deposits such as magnesium and calcium on metal surfaces. It is assumed that $OH^-$ ions are generated close to the metal surface as a result of cathodic protection and generated $OH^-$ ions increases the pH of the metal/seawater interface outlined as the following formulae. (1) $O_2+2H_2O+4e{\rightarrow}4OH^-$, or (2) $2H_2O+2e{\rightarrow}H_2+2OH^-$. And high pH causes precipitation of $Mg(OH)_2$ and $CaCO_3$ in accordance with the following formulae. (1) $Mg^{2+}+2OH^-{\rightarrow}Mg(OH)_2$, (2) $Ca^{2+}+CO{_3}^{2-}{\rightarrow}CaCO_3$. The focus of this study was to increase the amount of $CO{_3}^{2-}$ with the injection of $CO_2$ gas to the solution for accelerating process of the following formulae. (1) $H_2O+CO_2{\rightarrow}H_2CO_3$, (2) $HCO^{3-}{\rightarrow}{H^+}+CO{_3}^{2-}$. Electrodeposit films were formed by an electro-deposition technique on steel substrates in solutions of both natural seawater and natural seawater dissolved $CO_2$ gas with different current densities, over different time periods. The contents of films were investigated by scanning electron microscopy(SEM) and X-ray diffraction(XRD). The adhesion and corrosion resistance of the coating films were evaluated by anodic polarization. From an experimental result, only $CaCO_3$ were found in solution where injected $CO_2$ gas regardless of current density. In case of injecting the $CO_2$ gas, weight gain of electrodeposits films hugely increased and it had appropriate physical properties.
Ti and Ti-alloys have good biocompatibility, appropriate mechanical properties and excellent corrosion resistance. However, the widely used Ti-6Al-4V is found to release toxic ions (Al and V) into the body, leading to undesirable long-term effects. Ti-6Al-4V has much higher elastic modulus (100 GPa) than cortical bone (20 GPa). Therefore, titanium alloys with low elastic modulus have been developed as biomaterials to minimize stress shielding. The electrochemical behavior of surface-modified and MC3T3-E1 cell-cultured Ti-30(Nb,Ta) alloys with low elastic modulus have been investigated using various electrochemical methods. Surfaces of test samples were treated as follows: $0.3{\mu}m$ polished; $25{\mu}m$, $50{\mu}m$ and $125{\mu}m$ sandblasted. Specimen surfaces were cultured with MC3T3-E1 cells for 2 days. Average surface roughness ($R_a$) and morphology of specimens were determined using a surface profilometer, OM, and FE-SEM. Corrosion behavior was investigated using a potentiostat(EG&G PARSTAT 2273), and electrochemical impedance spectroscopy was performed (10 mHz to 100 kHz) in 0.9% NaCl solution at $36.5{\pm}1^{\circ}C$. The microstructures of the Ti-30(Ta,Nb) alloys had a needle-like appearance. The $R_a$ of polished Ti-30Ta and Ti-30Nb alloys was lower than that of the sandblasted Ti alloy. Cultured cells displayed round shapes. For polished alloy samples, cells were well-cultured on all surfaces compared to sandblasted alloy samples. In sandblasted and cell-cultured Ti-30(Nb,Ta) alloy, the pitting potential decreased and passive current density increased as $R_a$ increased. Anodic polarization curves of cell-cultured Ti alloys showed unstable behavior in the passive region compared to non-cell-cultured alloys. From impedance tests of sandblasted and cell-cultured alloys, the polarization resistance decreased as $R_a$ increased, whereas, $R_a$ for cell-cultured Ti alloys increased compared to non-cell-cultured Ti alloys.
The trend of poisoning of reforming catalyst along with the position of anodic catalyst bed was studied. Keeping the conditions that steam to carbon ratio was 2.5, operating voltage was 0.75 V, current density was $140mA/cm^2$, the unit cell was operated during 24 hrs at a steady state. And then the cell was stopped, the catalysts packed in the position of inlet, middle and outlet were sampled individually and then the amount of carbon, Li and K poisoned were analysed. After 100 hrs operated, the catalysts at the same positions were analysed at the same manner. The result of this experiment was as followings. After 24 hrs operated, the poisoning amounts of Li and K in the catalyst were 0.27 wt% at inlet, 0.23 wt% at middle and the highest value 1.59 wt% at outlet. After 100 hrs, the amount of poisoning is the highest in the catalyst packed at the inlet of unit cell. The performance simulation of unit cell explained these trends of poisoning catalysts. The simulation told that the catalyst in the region of the inlet of unit cell treated the 90% of initial methane flow rate and the highest electrochemical reaction happened in this region. So the catalysts of this region were the most poisoned with carbon, Li and K and also the rate of poisoning is faster than that of the catalyst at other regions. The temperature at the region of outlet of unit cell was $30^{\circ}C$ higher than that of other regions, so more Li, and K vaporized than at other regions and little reforming reaction at this region made the catalysts poisoning rate low.
Recently, the fuel oil of diesel engines of marine ships has been increasingly changed to heavy oil of low quality as the oil price is getting higher and higher. Therefore, the spiral gear attached at the motor of the oil purifier which plays an important role to purify the heavy oil is also easy to expose at severe environmental condition due to the purification of the heavy oil in higher temperature. Thus, the material of the spiral gear requires a better mechanical strength, wear and corrosion resistance. In this study, the heat treatment(tempering) with various holding time at temperature of $500^{\circ}C$ was carried out to the alloy of Cu-7Al-2.5Si as centrifugal casting, and the properties of both hardness and corrosion resistance with and without heat treatment were investigated with observation of the microstructure and with electrochemical methods, such as measurement of corrosion potential, cathodic and anodic polarization curves, cyclic voltammogram, and a.c. impedance. in natural seawater solution. The ${\alpha}$, ${\beta}^{\prime}$ and ${\gamma}_2$ phases were observed in the material in spite of no heat treatment due to quenching effect of a spin mold. However, their phases, that is, ${\beta}^{\prime}$ and ${\gamma}_2$ phases decreased gradually with increasing the holding time at a constant temperature of $500^{\circ}C$. The hardness more or less decreased with heat treatment, however its corrosion resistance was improved with the heat treatment. Furthermore, the longer holding time, the better corrosion resistance. In addition, when the holding time was 48hrs, its corrosion current density showed the lowest value. The pattern of corroded surface was nearly similar to that of the pitting corrosion, and this morphology was greatly observed in the case of no heat treatment. It is considered that ${\gamma}_2$ phase at the grain boundary was corroded preferentially as an anode. However, the pattern of general corrosion exhibited increasingly due to decreasing the ${\gamma}_2$ phase with heat treatment. Consequently, it is suggested that the corrosion resistance of Cu-7Al-2.5Si alloy can be improved with the heat treatment as a holding time for 48 hrs at $500^{\circ}C$.
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