• Journal of the Korean institute of surface engineering
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• v.43 no.6
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• pp.297-303
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• 2010

The effect of solution acidity and organic additives, polyethylene glycol (PEG), on the trivalent chromium electroplating was systematically investigated in the view point of electroreduction of trivalent chromium ions and solution stability. It was found that solution acidity controlled at pH 2.5 showed the widest current range for bright electrodeposits in the presence of PEG additives, which reduced the local current intensification at high current densities. Through complex interaction between PEG additives and hydrogen ion, that is, solution acidity, electrode potential was moved in the negative direction in the bulk solution, while it shifted in the positive when electric potential was scanned. In conjunction with electrochemical quartz crystal microbalance (EQCM), it was found that PEG additives had a role in promoting the electron transfer to trivalent chromium ion complexes in bulk solution and their adsorption at the electrode surface as well as interfering with hydrogen ion reduction process below pH 2.5. The PEG additives developed the nodular morphology during electroreduction of trivalent chromium ions with the increase of solution acidity and enhanced its current efficiency by maintaining the consumption of complexant, formic acid, at low speed.

• Journal of the Korea Convergence Society
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• v.8 no.11
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• pp.307-312
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• 2017

In the industry, galvanizing using the principle of sacrificial anode is used Zn-Ni alloy plating was developed as one of the measures to increase the corrosion resistance rather than pure zinc plating. The alloy plating layer has a corrosion resistance of 4-5 times that of the pure zinc plating layer, so that it is applied to automotive parts requiring high corrosion resistance even though the plating cost is high. The amount of Zn-Ni alloy plating solution is a sulfuric acid bath, a chlorinated bath, an alkali bath, and an ammonia bath. Here, the influence of the electrolytic conditions on the composition of the alloy plating in the chloride bath was investigated. The results are explained by the cathode overvoltage and the diffusion coefficient. In general, as the overvoltage of the cathode increases, the concentration polarization becomes more important than the activation polarization. The concentration polarization is determined by element diffusion in the diffusion layer. That is, as the overvoltage of the cathode increases, the Zn content having a large diffusion coefficient increases.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.77-77
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• 2018

Panel level packaging (PLP) 공정은 차세대 반도체 패키징 기술로써 wafer level packaging 대비 net die 면적이 넓어 생산 단가 절감에 유리하다. PLP 공정에 적용되는 구리 재배선 층 (RDL, redistribution layer)은 두께 불균일도에 의해 전기 저항의 유동이 민감하게 변화하기 때문에 RDL의 두께를 균일하게 형성하는 것은 신뢰성 측면에서 매우 중요하다. 구리 RDL은 주로 도금 공정을 통해 형성되며, 균일한 도금막 형성을 위해 도금조에 평탄제를 첨가하여 도금 속도를 균일하게 한다. 도금막에 대한 흡착은 주로 평탄제의 imine 작용기에 포함된 질소 원자가 관여하며, imine 작용기의 4차화에 의한 평탄제의 흡착 정도를 제어하여 평탄제 성능을 개선할 수 있다. 본 연구에서는 도금 평탄제에 포함된 imine 작용기의 질소 원자를 4차화하여 구리 RDL의 도금 두께 불균일도를 제어하고자 하였다. 유기첨가제와 4차화 반응을 위해 알킬화제로써 dimethyl sulfate의 비율을 조절하여 각각 0, 50, 100 %로 4차화 반응을 진행하였다. 평탄제의 4차화 여부를 확인하기 위해 gel permeation chromatography (GPC) 분석을 실시하였다. 도금은 20 ~ 200 um의 다양한 배선 폭을 갖는 구리 RDL 미세패턴에서 진행하였으며, 4차화 평탄제를 첨가하여 광학 현미경과 공초점 레이저 현미경을 통해 도금막 표면과 두께에 대한 분석을 실시하였다. GPC 분석을 통해 4차화 반응 후 알킬화제에 의해 나타나는 GPC peak이 감소한 것을 확인하였다. 광학 현미경 및 공초점 레이저 현미경 분석 결과, 4차화된 질소 원자가 존재하지 않는 평탄제의 경우, 도금 시 도금막의 두께가 불균일하였으며 단면 분석 시 dome 형태가 관찰되었다. 또한 100 % 4차화를 실시한 평탄제를 첨가하여 도금 한 경우 마찬가지로 두께가 불균일한 dish 형태의 도금막이 형성되었다. 반면, 50 % 4차화를 적용한 평탄제를 첨가한 경우, 도금막 단면의 형태는 평평한 모습을 보였으며 매우 양호한 균일도를 가지는 것으로 확인되었다. 이로 인해 imine 작용기를 포함한 평탄제의 4차화 반응을 통해 구리 RDL의 단면 형상 및 불균일도가 제어되는 것을 확인하였으며, 4차화된 imine 작용기의 비율을 조절하여 높은 균일도를 갖는 구리 RDL 도금이 가능한 것으로 판단되었다.

• Corrosion Science and Technology
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• v.11 no.6
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• pp.275-279
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• 2012

Ni-W alloy deposits have lately attracted the interest as an alternative surface treatment method for hard chromium electrodeposits because of higher wear resistance, hardness at high temperature, and corrosion resistance. This study deals with influences of process variables, such as electodeposition current density, plating temperature and pH, on the internal stress of Ni-W nanocrystalline deposits. The internal stress was increased with increasing the applied current density. With increasing applied current density, the grain size of the deposit decreases and concentration of hydrogen in the deposit increases. The subsequent release of the hydrogen results in shrinkage of the deposit and the introduction of tensile stress in the deposit. Consequently, for layers deposited at high current density, cracking occurs readily owing to high tensile stress value. By increasing the temperature of the electrodeposition from $60^{\circ}C$ to $80^{\circ}C$, the internal stress was decreased. It seems that an increase in the number of active ions overcoming the activation energy at elevated temperature caused a decline in the concentration polarization and surface diffusion. It decreased the level of hydrogen absorption due to the lessened hydrogen evolution reaction. Therefore, the lower level of hydrogen absorption degenerated the hydride on the surface of the electrode, resulting in the reduction of the internal stress of the deposits. By increasing the pH of the electrodeposition from 5.6 to 6.8, the internal stress in the deposits were slightly decreased. It is considered that the decrease in internal stess of deposits was due to supply of W complex compound in cathode surface, and hydrogen ion resulted from decrease of activity.

• Journal of the Korean institute of surface engineering
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• v.48 no.6
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• pp.260-268
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• 2015

The thermal barrier coating (TBC) for inner wall of liquid-fuel rocket combustor consists of NiCrAlY as bonding layer and $ZrO_2$ as a top layer. In most case, the plasma spray coating is used for TBC process and this process has inherent possibility of cracking due to large difference in thermal expansion coefficients among bonding layer, top layer and metal substrate. In this paper, we suggest crack-free TBC process by using a precise electrodeposition technique. Electrodeposited Ni-P/Cr double layer has similar thermal expansion coefficient to the Cu alloy substrate resulting in superior thermal barrier performance and high temperature oxidation resistance. We studied the effects of phosphorous concentrations (2.12 wt%, 6.97 wt%, and 10.53 wt%) on the annealing behavior ($750^{\circ}C$) of Ni-P samples and Cr double layered electrodeposits. Annealing temperature was simulated by combustion test condition. Also, we conducted SEM/EDS and XRD analysis for Ni-P/Cr samples. The results showed that the band layers between Ni-P and Cr are Ni and Cr, and has no formed with heat treatment. These band layers were solid solution of Cr and Ni which is formed by interdiffusion of both alloy elements. In addition, the P was not found in it. The thickness of band layer was increased with increasing annealing time. We expected that the band layer can improve the adhesion between Cr and Ni-P.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.139-139
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• 2016

반도체 다마신배선용 도금용 구리도금첨가제는 대표적으로 accelerator, suppressor 및 leveler 첨가제를 사용하여 다마신 패턴을 채우고 평탄화를 시킬 수 있다. Si 반도체 공정기술에 기반한 정확한 구조분석을 통해 각각의 첨가제의 기능이 비교적 체계적으로 연구되었으며, 최근에는 유속영향을 많이 받는 것으로 알려진 leveler 첨가제에 대한 연구가 활발히 진행되고 있다. 본 연구는 대표적 leveler 첨가제의 하나인 Janus Green B(JGB, $C_{30}H_{31}ClN_6$)를 0 ~ 1 mM을 첨가하여 Si 기판위에 증착된 Cu 씨드층 상의 도금후 표면상태 및 불순물의 농도를 분석하고, 이 박막층들의 결정립 성장 경향성을 electron backscattered diffraction(EBSD) 분석을 통해 진행하였다. C, H, N 등의 불순물이 JGB 농도와 선형적 관계를 가지고 증가하는 것을 알 수 있었으며, S와 O의 불순물도 JGB 농도 증가에 따라 증가하는 것을 알 수 있었다. 또한 0.1 mM 첨가한 경우에 60% 정도 결정립 성장이 진행된 것을 알 수 있었으며, 0.2 mM을 넣은 경우에는 결정립 성장이 일어나지 않은 것을 알 수 있었다. 흥미로운 점은 4 point probe를 통한 면저항 측정을 통해 EBSD를 통한 결정립성장이 관찰되지 않은 0.2 mM JGB를 첨가한 경우에 대해서도 면저항의 감소가 관찰되며, 오히려 JGB 농도가 높을수록 이러한 면저항의 감소가 빠르게 시작되는 것을 관찰할 수 있었다. 이는 JGB 농도 증가에 따라 박막층의 불순물의 농도가 증가하고 막내에 존재하는 불순물의 농도가 증가하면 내부응력장이 커짐으로 인해 더욱 빠른 속도로 불순물의 재배치가 일어난 것으로 보인다. 이러한 불순물이 결정립계면에 편석되는 경우에 pinning을 통해 결정립계면의 이동을 저하시킬 수 있으므로 결정립의 성장 억제가 가능해진 것으로 판단된다.

• Corrosion Science and Technology
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• v.5 no.5
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• pp.168-172
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• 2006

Alloy 600 having a superior resistance to a corrosion is used as a steam generator tubing in nuclear power plants. In spite of its high corrosion resistance, there are many tubings which experience corrosion problems such as a SCC under the high temperature and high pressure environments of nuclear power plants. The Alloy 600 tubing can be repaired by using a Ni electroplating having an excellent SCC resistance. In order to carry out a successful Ni electrodeposition inside a steam generator tubing, the effects of various parameters on the material properties of the electrodeposit should be elucidated. Hence this work deals with the effects of an applied current density, duty cycle($T_{on}/(T_{on}+T_{off})$) of a pulse current, bath temperature and solution pH on the material properties of Ni electrodeposit obtained from a Ni sulphamate bath by analyzing the current efficiency, potentiodynamic curve, hardness and stress-strain curve. Hardness, YS(yield strength) and TS(tensile strength) decreased whereas the elongation increased as the applied current density increased. This was thought to be by a concentration depletion at the interface of the electrodeposit/solution, and a fractional decrease of the hydrogen reduction reaction. As the duty cycle increased, the hardness, YS and TS decreased while the elongation increased. During an off time at a high duty cycle, the concentration depletion could not be recovered sufficiently enough to induce a coarse grain sized electrodeposit. With an increase of the solution temperature and pH, the YS and TS increased while the elongation decreased. The experimental results of the hardness and the stress-strain curves can be supplemented by the results of the potentiodynamic curve.

• Corrosion Science and Technology
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• v.6 no.5
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• pp.233-238
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• 2007

Due to the occasional occurrence of a localizedcorrosion such as a SCC and pitting in steam generator tubing(Alloy 600), leading to a significant economical loss, an effective repair technology is needed. For a successful electrodeposition inside a tube, many processes should be developed. Among these processes, an anode to be installed inside a tube, a degreasing condition to remove any dirt and grease, an activation condition for a surface oxide elimination, a strike layer forming condition which needs to be adhered tightly between an electroforming layer and a parent tube and a condition for an electroforming layer should be established. Through a combination of these various process condition parameters, the desired material properties can be acquired. Among these process parameters, various material properties including a mechanical property and its variation along with the height of the electrodeposit inside a tube as well as its thermal stability and SCC resistance should be assessed for an application in a plant. This work deals with the material properties of the Ni electrodeposits formed inside a tube by using the anode developed in this study such as the current efficiency, hardness, tensile property, thermal stability and SCC behavior of the electrodeposit in a 40wt% NaOH solution at $315^{\circ}C$. It was found that a variation of the material properties within the entire length of the electrodeposit was quite acceptable and the Ni electrodeposit showed an excellent SCC resistance.

• Resources Recycling
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• v.21 no.6
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• pp.45-50
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• 2012

The room-temperature electrodeposition of metallic lithium was investigated from ionic liquid, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13TFSI) with lithium bis (trifluoromethanesulfonyl)imide (LiTFSI) as a lithium source. Cyclic voltammograms on gold working electrode showed the possibility of the electrodeposition of metallic lithium, and the reduction current on a gold electrode was higher than the value on platinum and copper. The metallic lithium could be electrodeposited on the gold electrode under potentiostatic condition at -2.4 V (vs. Pt-QRE) and was confirmed by analytical techniques including XRD and SEM-EDS. The dendrite-typed electrodeposits were composed of a metallic lithium and a alloy with gold substrate. And any impurity could be detected except for trace oxygen introduced during handling for the analyses.

• Journal of the Korean institute of surface engineering
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• v.18 no.3
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• pp.125-133
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• 1985

About 1 mm thick nickel electrodeposits were obtained from nickel sulphamate baths at 40 to 60$^{\circ}C$ over the range of current densities form 5 to 25 A/$dm^2$. Deposits from above about 1.2V of cathode overpotential had randomly distributed fine grains due to a higher nucleation rate and hence had a high hardness. A deposit obtained at 0.63 V had the [110] orientation with a field oriented fine structure which yield a relatively high hardness. Deposite obtained at the intermediate overpotentials showed the [100] orientation with coarse field oriented structure whose column width tended to decrease with increasing cathode overpotential, which, in turn, gave rise to an increase in hardness. Residual stresses of the deposits measured by X-ray technique were mostly tensile but did not exceed 80 MPa, and were occasionally very small compressive. The cathode current efficiency was above 90% in all the electrolysis conditions, whereas the anode current efficiency varied from 50 to 90% with current density, bath temperature and nickel chloride concentration, among which the chloride was the most influential.