• Corrosion Science and Technology
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• 제6권2호
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• pp.50-55
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• 2007

The smaller size and higher integration of advanced electronic package systems result in severe electrochemical reliability issues in microelectronic packaging due to higher electric field under high temperature and humidity conditions. Under these harsh conditions, electronic components respond to applied voltages by electrochemical ionization of metal and the formation of a filament, which leads to short-circuit failure of an electronic component, which is termed electrochemical migration. This work aims to evaluate electrochemical migration susceptibility of the pure Sn, Sn-3.5Ag, Sn-3.0Ag-0.5Cu solder alloys in $Na_{2}SO_{4}$. The water drop test was performed to understand the failure mechanism in a pad patterned solder alloy. The polarization test and anodic dissolution test were performed, and ionic species and concentration were analyzed. Ag and Cu additions increased the time to failure of Pb-free solder in 0.001 wt% $Na_{2}SO_{4}$ solution at room temperature and the dendrite was mainly composed of Sn regardless of the solders. In the case of SnAg solders, when Ag and Cu added to the solders, Ag and Cu improved the passivation behavior and pitting corrosion resistance and formed inert intermetallic compounds and thus the dissolution of Ag and Cu was suppressed; only Sn was dissolved. If ionic species is mainly Sn ion, dissolution content than cathodic deposition efficiency will affect the composition of the dendrite. Therefore, Ag and Cu additions improve the electrochemical migration resistance of SnAg and SnAgCu solders.

• Bulletin of the Korean Chemical Society
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• 제17권9호
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• pp.802-807
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reactions of aryl benzoates (X-C6H4CO2C6H4-Y) with EtO-, Z-C6H4O- and Z-C6H4C(Me)=NO- in absolute ethanol at 25.0 ℃. All the reactions have been performed in the presence of excess 18-crown-6 ether in order to eliminate the catalytic effect shown by alkali metal ion. A good Hammett correlation has been obtained with a large ρ- value (-1.96) when σ- (Z) constant was used for the reaction of p-nitrophenyl benzoate (PNPB) with Z-C6H4O-. Surprisingly, the one for the reaction of PNPB with Z-C6H4C(Me)=NO- gives a small but definitely positive ρ- value (＋0.09). However, for reactions of C6H5CO2C6H4-Y with EtO-, correlation of log k with σ- (Y) constant gives very poor Hammett correlation. A significantly improved linearity has been obtained when σ0 (Y) constant was used, indicating that the leaving group departure is little advanced at the TS of the RDS. For reactions of X-C6H4CO2C6H4-4-NO2 with EtO-, C6H5O- and C6H5C(Me)=NO-, correlations of log k with σ (X) constants for all the three nucleophile systems give good linearity with large positive ρ values, e.g. 2.95, 2.81 and 3.06 for EtO-, C6H5O- and C6H5C(Me)=NO-, respectively. The large ρ values clearly suggest that the present reaction proceeds via a stepwise mechanism in which the formation of the addition intermediate is the RDS.

• Environmental Engineering Research
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• 제24권3호
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• pp.463-473
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• 2019

Nanoscale zero-valent iron (nZVI) has proved to be an effective tool in applied environmental nanotechnology, where the decreased particle diameter provides a drastic change in the properties and efficiency of nanomaterials used in water purification. However, the agglomeration and colloidal instability represent a problematic and a remarkable reduction in nZVI reactivity. In view of that, this study reports a simple and cost-effective new strategy for ultra-small (< 7.5%) distributed functionalized nZVI-EG (1-9 nm), with high colloidal stability and reduction capacity. These were obtained without inert conditions, using a simple, economical synthesis methodology employing two stabilization mechanisms based on the use of non-aqueous solvent (methanol) and ethylene glycol (EG) as a stabilizer. The information from UV-Vis absorption spectroscopy and Fourier transform infrared spectroscopy suggests iron ion coordination by interaction with methanol molecules. Subsequently, after nZVI formation, particle-surface modification occurs by the addition of the EG. Size distribution analysis shows an average diameter of 4.23 nm and the predominance (> 90%) of particles with sizes < 6.10 nm. Evaluation of the stability of functionalized nZVI by sedimentation test and a dynamic light-scattering technique, demonstrated very high colloidal stability. The ultra-small particles displayed a rapid and high nitrate removal capacity from water.

• 한국산학기술학회논문지
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• 제7권6호
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• pp.1313-1318
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• 2006

흑연 음극 표면상에 형성되는 필름의 생성 기구를 규명하기 위하여, 1 몰의 $LiPF_6$가 함유된 탄산에틸렌과 탄산디에칠의 혼합 용액 중에서 고배향성 열분해 흑연을 0.5 mV $s^{-1}$ 의 느린 속도로 전위주사하면서 원자력간 현미경을 이용하여 전극표면을 in-situ 관찰하였다. 전해질 용액의 분해반응은 전극의 스텝 모서리 상에서 우선적으로 진행되었으며, 전극 전위 2.15 V (vs. $Li^+$/Li) 에서 시작되었다. 0.95-0.8 V (vs. $Li^+$/Li) 의 전위 영역에서 전극 표면의 특정 부분이 평탄하게 부풀어오르는 현상과, 타원형의 돌기 구조가 관찰되었다. 이러한 형상 변화에 있어서 전자는 용매화된 리튬 이온이 흑연 층간에 삽입되며 나타나는 구조 변화이며, 후자는 삽입된 용매화 리튬이 환원 분해되어 생성된 것으로 추정된다. 0.8 V (vs. $Li^+$/Li) 보다 음의 전위 영역에서는 입자상의 침전물이 전극 표면에 형성되었다. 1 사이클 후, 측정된 침전층의 두께는 30 nm 이었다. 이러한 침전물은 리튬염($LiPF_6$)과 용매 분자(EC 및 DEC)들이 분해되어 생성된 것이며, 전극 표면에서 계속적으로 전해질 용액이 분해되는 반응을 억제하는 중요한 역할을 하고 있는 것으로 생각된다.

• 대한화학회지
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• 제55권3호
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• pp.346-353
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• 2011

7-hydroxy-2H-chromen-2-one(HC)와 7-hydroxy-2H-chromen-2-one-4-acetic acid(HCA)의 염기성 가수분해반응을 aqueous-methanol과 aqueous-acetone 혼합물에서 283 K에서 313 K의 온도 범위에서 속도론적으로 연구하였다. 반응의 활성화 파라미터를 구하고 토의하였다. 게다가, 물, 물-에탄올, 물-아세톤 혼합물 내에서 화합물들에 대한 활성화 에너지 장벽의 변화를 속도론적 데이터로부터 추정하였다. 활성화 장벽의 변화는 HC and HCA의 가수분해 반응과 거의 같았다. HC와 HCA의 염기성 가수분해는 $k_{obs}=k_2[OH^-]$와 같은 속도법칙을 따른다. 메탄올 또는 아세톤의 비가 증가함에 따라 HC 와 HCA의 속도 상수들이 감소하는 것은 $OH^-$ 이온이 불안정해지기 때문이다. 활성화 엔트로피가 큰 음의 값을 갖는 다는 것은 반응이 중간 착물의 형성을 경유하며 진행된다는 것을 의미하며, 또한 중간 착물이 경직성과 안정도를 갖는다는 것을 의미한다. 그러므로, 중간 착물의 고리 열림이 속도 조절 단계가 될 것이다.

• 한국염색가공학회지
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• 제1권1호
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• pp.19-25
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• 1989

In past, dye diffusion and dyeing rate in fibers have been emphasized in dyeing phenomena. However, in the light of the properties of colloids in the surface of disperse phase and dispersion, there exist specific characters such as adsorption or electric double layer, which seems to play important roles in determining the physiochemical properties in the dyeing system. Electrostatic bonding, hydrogen bonding and Van der Waals adsorption are common in dyeing as well as covalent bonding. Particularly, electrostatic bonding is premised on the existance of ionic radicals in fibers. The present study was aimed to clarify the electrokinetic phenomena of dyeing through the role of electric double layer by ion in amphoteric fibers with different ionic effects under different pH. Spectrophotometric analysis method was used to compare dyeing condition of surface, which can be detected by electrokinetic phenomena and the inner of fibers after deceleration of dyed fibers. Nylon and wool, the typical amphoteric fibers were dyed with monoazo acid dyes such as C.I. Acid Orange 20, and C.I. Acid Orange 10. Various combinations were prepared by combining pH, temperature and dye concentration, in order to generate streaming electric potential which were measured by microvolt meter and specific conductivity meter. The results were transformed to zeta potential by Helmholtz-Smoluchowski formular and to surface electric charge density by Suzawa formular, surface dye amount, and effective surface area of fibers. The amount of dyes of inner fibers were also measured by the Lambert-Beer’s law. The main results obtained are as follows. 1. By measuring zeta pontential, it was possible to detect the dyeing mechanism, surface charge density, surface dye amount and effective surface area concerning dye adsorption of the amphoteric fibers. 2. Zeta pontential increases in negative at low pH and high dye concentration in the process of dyeing. This implied that there existed ionic bond formation in the dyeing mechanism between acid dyes and amphoteric fibers. 3. Dibasic acid dye had little changing rate in zeta potential due to the difference in solubility of dye and in number of dissociated ions per dye molecule to bond with amino radicals of amphoteric fibers. The dye adsorption of mono basic acid dye was higher than that of dibasic acid dye. 4. The effective surface areas concerning dyeing were $6.3E+05\;cm^2/g$ in nylon, $1.6E+07\;cm^2/g$ in wool fiber being higher order of wool then nylon.

• Restorative Dentistry and Endodontics
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• 제24권2호
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• pp.330-336
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• 1999

In biological systems, the mineral that forms hard tissue is of an apatitic nature, and hydroxyapatite($Ca_5OH(PO_4)_3$: HA) is generally considered as the prototype for such a mineral. Thus, the precipitation of HA, having biological implications, has been the subject of several investigations. Crystal growth studies using HA seeds in supersaturated solutions have enhanced our understanding of the process and mechanism involved in seeded crystal growth. From these studies, it has become apparent that the precipitation rate of HA onto the seed crystals depends on the various conditions, especially on the additives. The relation between the supersaturated solution containing fluoride and the process of HA crystal growth enhances the understanding of mechanism of HA crystal growth. Until recently, the studies have been on the crystal growth of enamel minerals and synthetic HA seeds in the supersaturated solution containing 1~2 ppm fluoride. The purpose of the present investigation is to study the effect that fluoride of high concentration has on the crystal growth kinetics of HA. In order to produce the composition found in the secretory enamel fluid, experimental solutions of 1mM Ca, 3mM P, and 100mM Tris as background electrolyte were used. Then this experimental solutions were added to 0, 2, 4, 6, 8, 10 ppm fluoride. The effect of fluoride at high concentrations on the precipitation was examined in a bench-top crystal growth model adopting a miniaturized reaction column. Chemical analysis was employed for characterization of working solutions before and after the experimentation. Remarkable findings were : 1) the amount of crystal growth was gradually accelerated as the fluoride concentration increased until 6 ppm, but decreased in 8 and 10 ppm fluoride; 2) the amount of fluoride ion consumed in crystal formation was constant despite the increase in fluoride concentration.

• 헤리티지:역사와 과학
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• 제53권1호
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• pp.24-33
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• 2020

출토 청동 유물에서는 매장 환경 내 공존하는 복합적인 부식 인자로 인해 다양한 형태와 색상의 부식 생성물이 관찰되며, 이러한 부식 생성물은 장기 부식의 정보뿐만 아니라 보존처리 시 중요한 자료가 될 수 있다. 따라서 청동 유물의 부식층 및 부식 생성물에 대한 과학적 분석을 실시하여 부식층 형성 과정 및 부식 생성물의 특성을 규명하고, 노출된 매장 환경의 특성 및 내부 부식 인자와의 연관성을 해석하는 연구가 필수적이다. 본 연구에서는 동일 유적에서 출토된 청동 유물을 합금비와 제작기법에 따라 분류 후, 표면·부식층·부식 생성물에 대한 종합적인 분석을 실시하여 청동 유물의 부식 메커니즘과 부식층 형성 과정, 부식 생성물의 특성에 대해 알아보고자 하였다. 분석 대상으로 선정된 총 5점의 시료는 합금비 및 제작기법 분석 결과에 따라 2개의 그룹으로 구분되는데, Cu-Sn-Pb합금으로 열처리가 진행되지 않은 Group 1은 내·외측 중 일부 또는 양측에 외부 부식층이 형성되어 있으며, 표면은 녹색 또는 청색으로 확인되었다. 소지 금속에서는 α상, α+δ상 선택 부식이 일어나는 것을 알 수 있었으며, α+δ상 선택 부식 후 빈 공간에 순도가 98% 이상인 Cu가 농축되어 있는 현상이 확인되었다. Cu-Sn합금으로 열처리가 진행된 Group 2는 외부 부식층이 형성되지 않았으며, 표면이 어두운 황색으로 관찰되었다. 또한 Group 1과는 다르게 소지 금속 내부에서 α상 선택 부식이 발생한 것을 확인하였다. 연구결과를 종합해 볼 때 동일한 유적에서 출토된 청동 유물에서도 합금비 및 제작기법에 따라 부식층 형성과정 및 부식 생성물의 형태와 색상, 금속이온 이동경로 등 여러 측면에서 차이를 나타냄을 알 수 있다. 또한 동일 유물에서도 부분적으로 서로 다른 부식 특성을 보이기도 하는데 이는 매장 환경 내 노출 환경에 따라 다른 형태의 부식이 발생할 수 있음을 뜻한다. 따라서 동일 유적에서 출토된 청동 유물이라 하더라도 합금비, 제작기법, 노출 환경에 따라 부식 특성이 다를 것이라고 판단된다. 본 연구는 특정 지역 및 유물을 대상으로 한 부식 특성의 일면을 보여주는 것이므로 향후 여러 지역에서 출토되는 청동 유물의 부식층 및 부식 생성물 특성에 대한 연구를 통해 매장 환경에 따른 부식 메커니즘에 대한 심층적인 연구가 필요할 것으로 판단된다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
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• pp.222-222
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• 2012

Metal oxide gas sensors based on semiconductor type have attracted a great deal of attention due to their low cost, flexible production and simple usability. However, most works have been focused on n-type oxides, while the characteristics of p-type oxide gas sensors have been barely studied. An investigation on p-type oxides is very important in that the use of them makes possible the novel sensors such as p-n diode and tandem devices. Monoclinic cupric oxide (CuO) is p-type semiconductor with narrow band gap (~1.2 eV). This is composed of abundant, nontoxic elements on earth, and thus low-cost, environment-friendly devices can be realized. However, gas sensing properties of neat CuO were rarely explored and the mechanism still remains unclear. In this work, the neat CuO layers with highly ordered mesoporous structures were prepared by a template-free, one-pot solution-based method using novel ink solutions, formulated with copper formate tetrahydrate, hexylamine and ethyl cellulose. The shear viscosity of the formulated solutions was 5.79 Pa s at a shear rate of 1 s-1. The solutions were coated on SiO2/Si substrates by spin-coating (ink) and calcined for 1 h at the temperature of $200{\sim}600^{\circ}C$ in air. The surface and cross-sectional morphologies of the formed CuO layers were observed by a focused ion beam scanning electron microscopy (FIB-SEM) and porosity was determined by image analysis using simple computer-programming. XRD analysis showed phase evolutions of the layers, depending on the calcination temperature, and thermal decompositions of the neat precursor and the formulated ink were investigated by TGA and DSC. As a result, the formation of the porous structures was attributed to the vaporization of ethyl cellulose contained in the solutions. Mesoporous CuO, formed with the ink solution, consisted of grains and pores with nano-meter size. All of them were strongly dependent on calcination temperature. Sensing properties toward H2 and C2H5OH gases were examined as a function of operating temperature. High and fast responses toward H2 and C2H5OH gases were discussed in terms of crystallinity, nonstoichiometry and morphological factors such as porosity, grain size and surface-to-volume ratio. To our knowledge, the responses toward H2 and C2H5OH gases of these CuO gas sensors are comparable to previously reported values.

• Journal of Applied Biological Chemistry
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• 제52권1호
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• pp.28-32
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• 2009

세균독소인 톨라신은 재배버섯에서 버섯균사 및 자실체의 구조를 파괴하여 갈반병을 일으킨다. 톨라신의 세포독성은 톨라신이 적혈구의 세포막에 pore를 형성하여 세포구조를 파괴하기 때문에 용혈활성을 측정하여 평가한다. 저자들은 $Zn^{2+}$와 $Cd^{2+}$에 의한 톨라신의 용혈활성 저해효과를 측정하는 중에 $Ni^{2+}$이 또 다른 저해제로 톨라신의 독성을 억제하는 것을 발견하였다. $Ni^{2+}$에 의한 톨라신 용혈활성의 저해는 농도의존적이었으며, Ki 값은 대략 10mM이었고, 이것은 $Ni^{2+}$이 $Cd^{2+}$에 비하여 저해효과가 높음을 의미한다. 용혈활성은 50mM 이상의 $Ni^{2+}$농도에서 완전히 제거되었으며, $Ni^{2+}$의 효과는 EDTA 첨가에 의해 가역적임을 확인하였다. 톨라신에 의한 용혈활성이 20mM $Ni^{2+}$에 의해서 완전히 억제된 상태에서 EDTA를 가하면 즉각 용혈활성이 나타났다. $Ni^{2+}$에 의한 톨라신 독성의 저해기작은 알 수 없지만, $Ni^{2+}$은 톨라신의 독성과정인 막결합, 분자중합체 형성, pore 형성, pore를 통한 막대한 양의 이온이동 등에 작용할 수 있을 것이다. 된 연구의 결과는 $Ni^{2+}$이 독성과정의 마지막 단계인 pore를 통한 이온이동 과정을 저해함을 보여준다.