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Synthesis and Characterization of Various Di-N-Functionalized Tetraaza Macrocyclic Copper(II) Complexes

  • Kang, Shin-Geol;Kim, Na-Hee;Lee, Rae-Eun;Jeong, Jong-Hwa
    • Bulletin of the Korean Chemical Society
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    • v.28 no.10
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    • pp.1781-1786
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    • 2007
  • Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.

Electrical Conductivity by Addition of Zn and Cu on Mg-Zn-Cu Alloys (Mg-Zn-Cu 합금의 Zn, Cu 첨가량에 따른 전기전도도 특성)

  • Ye, Dae-Hee;Kim, Hyun-Sik;Kang, Min-Cheol;Kim, Jung-Dae;Jeoung, Hae-Yong
    • Journal of Korea Foundry Society
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    • v.34 no.3
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    • pp.100-106
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    • 2014
  • In recent years, Mg and its alloys have attracted a great deal of attention due to their low density, relatively excellent castability, and straightforward recyclability. Mg alloys have been widely applied to various industrial fields, and are representatively used in automotive and electronic parts. According to previous researches, the electrical conductivity of Mg alloys greatly decreases with increasing Al content. However, with the addition of Zn and/or Cu, the electrical conductivity of Mg alloys is maintained or slightly increased, and improved mechanical properties are obtained as well. On this basis, Mg-Zn-Cu alloys have been investigated in the present study with a focus on the effect of adding Zn and Cu on the electrical conductivity. The Zn and Cu contents ranged from 4 to 6wt.% and 0 to 1.5wt.%, respectively. Ternary Mg-Zn-Cu alloys have been prepared by gravity casting in a steel mold. In the as-casting condition, the electrical conductivity of Mg-Zn-Cu alloys showed a linear increasing trend with decreasing Zn and increasing Cu contents. Furthermore, impact values of Zn = -1.5 and Cu = 2.5 were determined for these alloys by electrical conductivity tests.

Effects of Supplementary Mineral Methionine Chelates (Zn, Cu, Mn) on the Performance and Eggshell Quality of Laying Hens

  • Lim, H.S.;Paik, I.K.
    • Asian-Australasian Journal of Animal Sciences
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    • v.16 no.12
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    • pp.1804-1808
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    • 2003
  • A layer experiment was conducted to determine the effects of supplementary methionine chelates (Cu, Zn and Mn), individual or in combination, on laying performance, eggshell quality, gizzard erosion, and IgG level of serum for 8 weeks. Five hundred 96-wk-old force molted ISA Brown layers were assigned to five dietary treatments. Basal diet was formulated to meet or exceed the nutrients requirements listed in NRC (1994). Five experimental diets were control, Zn-methionine chelate (Zn-Met) supplemented, Cumethionine chelate (Cu-Met) supplemented, Zn-Mn-methionine chelate (Zn-Mn-Met) supplemented and Zn-Mn-Cu-Met supplemented diet. Each treated diet was supplemented with respective mineral(s) at the level of 100 ppm in the form of methionine chelate. Egg production was increased by Cu-Met supplementation but decreased by Zn-Met supplementation. Egg weight was significantly (p<0.05) lower in Cu-Met treatment than those of the control and Zn-Met treatment. Specific gravity of eggs and eggshell strength were highest and soft egg production was lowest in Cu-Met treatment. Gizzard erosion index was significantly increased by supplementation of Cu-Met, Zn-Mn-Met or Zn-Mn-Cu-Met. Zinc content in liver significantly increased by Zn-Met, but not by Zn-Mn-Cu-Met treatment. In conclusion, 100 ppm Cu in Cu-Met chelate improved laying performance and eggshell quality but also increased gizzard erosion index. Supplementation of Zn-Met or its combination with other mineral chelates had no beneficial effects on laying performance and eggshell quality.

A Characteristic of Microstructures in Bonding Interlayer of Brazed Titanium to Copper (브레이징한 Ti/Cu 접합계면부의 미세조직 특성)

  • 김우열;정병호;이성렬
    • Journal of Welding and Joining
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    • v.13 no.3
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    • pp.106-115
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    • 1995
  • To know the bonding phenomena of Ti/Cu brazed joint, a characteristic of microstructures in bonding interlayer of vacuum brazed pure Ti to Cu has been studied in the temperature range from 1088 to 1133K for various bonding times using Ag-28wt%Cu filler metal. Also intermediate phases formed in bonded interlayer and behavior of layer growth have been investigated. The obtained results in this study are as follows: 1) Liquid insert metal width at the each brazing temperature was proportional to the square root of brazing time, and it was considered that the liquid insert metal width was controlled by the diffusion rate process of primary .alpha.-Cu formed at the Ti side. 2) Intermediate phases formed near the Ti interface were .betha.-Ti and intermetallic compounds TiCu, Ti$_{2}$Cu, Ti$_{3}$Cu, and TiCu. 3) .betha.-Ti formed in Ti base metal durig brazing transformed to lamellar structure, .alpha.-Ti + Ti$_{2}$Cu. The structure came from the eutectoil decomposition reaction in cooling. And the width of .betha.-Ti layer was proportional to the square root of brazing time, and it was considered that the growth of .betha.-Ti layer was controlled by interdiffusion rate process in .betha.-Ti. 4) The layer growth of TiCu, Ti$_{3}$Cu$_{4}$ and TiCu, phases formed near the Ti interface was linerface was linearly proportional to the brazing time, and it was considered that the layer growth of these phases was controlled by the chemical reaction rate at the interface.

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A Study on the Optimized Copper Electrochemical Plating in Dual Damascene Process

  • Yoo, Hae-Young;Chang, Eui-Goo;Kim, Nam-Hoon
    • Transactions on Electrical and Electronic Materials
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    • v.6 no.5
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    • pp.225-228
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    • 2005
  • In this work, we studied the optimized copper thickness in Cu ECP (Electrochemical Plating). In order to select an optimized Cu ECP thickness, we examined Cu ECP bulge (bump, hump or over-plating amount), Cu CMP dishing and electrical properties of via hole and line trench over dual damascene patterned wafers split into different ECP Cu thickness. In the aspect of bump and dishing, the bulge increased according as target plating thickness decreased. Dishing of edge was larger than center of wafer. Also in case of electrical property, metal line resistance distribution became broad gradually according as Cu ECP thickness decreased. In conclusion, at least $20\%$ reduced Cu ECP thickness from current baseline; $0.8\;{\mu}m$ and $1.0\;{\mu}m$ are suitable to be adopted as newly optimized Cu ECP thickness for local and intermediate layer.

Effect of Cu2+ Concentration and Additives on Properties of Electrodeposited Cu Thin Films for FCCL from Sulfate Baths (황산염용액으로부터 전기도금 된 FCCL용 Cu 필름의 특성에 미치는 Cu 이온농도 및 첨가제의 영향)

  • Shin, Dong-Yul;Park, Doek-Yong;Koo, Bon-Keup
    • Journal of the Korean institute of surface engineering
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    • v.42 no.5
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    • pp.191-196
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    • 2009
  • Nanocrystalline Cu thin films were electrodeposited from sulfate baths and investigated systematically the influences of $Cu^{2+}$ concentration and additives on current efficiency, residual stress, surface morphology, and XRD patterns of electrodeposited Cu film. Current efficiency was nearly 100% at from 0.2M to 1.0 M $Cu^{2+}$ concentration. but it was linearly increased with $Cu^{2+}$ concentration at less than 0.2M. The residual stress was observed in range of 7.9 to 18.4 MPa and tensile stress mode. Dendritic and powdered form was obtained at below 0.1 M. As increased with $Cu^{2+}$ concentration in solution, the main peak in the XRD pattern shifted (111) and (220) from (200). In the other hand, all about 100% current efficiency observed in all additive concentration systems, and residual stress observed in range of 20.4 to 26.3 MPa tensile stress. The condition 5(Ultra make-up - 10 ml/l, Ulta A - 0.5ml/l, Ultr B - 0.5 ml/l) was good surface morphology, and fcc(111) peak in XRD patterns increased with increasing additive concentration.

Effect of under-bump-metallization structure on electromigration of Sn-Ag solder joints

  • Chen, Hsiao-Yun;Ku, Min-Feng;Chen, Chih
    • Advances in materials Research
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    • v.1 no.1
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    • pp.83-92
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    • 2012
  • The effect of under-bump-metallization (UBM) on electromigration was investigated at temperatures ranging from $135^{\circ}C$ to $165^{\circ}C$. The UBM structures were examined: 5-${\mu}m$-Cu/3-${\mu}m$-Ni and $5{\mu}m$ Cu. Experimental results show that the solder joint with the Cu/Ni UBM has a longer electromigration lifetime than the solder joint with the Cu UBM. Three important parameters were analyzed to explain the difference in failure time, including maximum current density, hot-spot temperature, and electromigration activation energy. The simulation and experimental results illustrate that the addition 3-${\mu}m$-Ni layer is able to reduce the maximum current density and hot-spot temperature in solder, resulting in a longer electromigration lifetime. In addition, the Ni layer changes the electromigration failure mode. With the $5{\mu}m$ Cu UBM, dissolution of Cu layer and formation of $Cu_6Sn_5$ intermetallic compounds are responsible for the electromigration failure in the joint. Yet, the failure mode changes to void formation in the interface of $Ni_3Sn_4$ and the solder for the joint with the Cu/Ni UBM. The measured activation energy is 0.85 eV and 1.06 eV for the joint with the Cu/Ni and the Cu UBM, respectively.

Changes of Chemical Species in Soil Solution Induced by Heavy Metals (중금속이 토양용액 중 화학종 변화에 미치는 영향)

  • Yang, Jae-E.;Lee, Ki-Won;Kim, Jeong-Je;Lim, Hyung-Sik
    • Korean Journal of Environmental Agriculture
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    • v.14 no.3
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    • pp.263-271
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    • 1995
  • Chemical assessment of soil pollution with heavy metals was made by analyzing the changes in pH, ionic strength, cationic concentration and chemical species in the soil solution. Saturated pastes of the unpolluted soils were made by adding solutions containing Cu or Cd and the final Cu or Cd concentrations were in the range of 0 to 400 mg/kg. After equilibrating for 24 hours at $25^{\circ}C$, the soil solution was extracted from the saturated pastes by the vacuum extraction method and analyzed for pH, electrical conductivity, Cu, Cd, cations and inorganic ligands. Chemical species in soil solution were calculated by the GEOCHEM-PC program employing the input variables of pH, ionic strength(${\mu}$), molar concentrations of cations and ligands. Increasing Cu or Cd additions lowered pH of the soil solution but increased concentrations of Ca, Mg and K resulting in increases of ${\mu}$ of the soil solution. Effects of Cu on lowering pH and increasing ${\mu}$ were greater than those of Cd. Concentrations of Cu or Cd in soil solution were relatively very low as compared to those of additions, but increased linearly with increasing additions representing that concentrations of Cu were higher than those of Cd. At 400 mg/kg additions, concentrations of Cu were in the range of 0.51 to 11.70 mg/L but those of Cd were 34.4 to 88.5 mg/L. Major species of Ca, Mg and K were free ions and these species were equivalent to greater than 95 molar % of the existing respective molar concentrations. These cationic species were not changed by Cu or Cd additions. Major species of Cu in lower pH soils such as SiCL and SL were free $Cu^{2+}$ (>95 molar %), but those in LS having a higher pH were free $Cu^{2-}$ and Cu-hydroxide complex. At 100 mg Cu/kg treatment, $Cu^{2+}$ and Cu-hydroxide complex were equivalent to 73 and 22.4 molar %, respectively. These respective percentages were decreased and increased correspondingly with increasing Cu treatments. Major species of Cd in soil solution were free $Cd^{2+}$ and Cd-chloride complex, representing 79 to 85 molar % for $Cd^{2+}$ and 13 to 20% for Cd-chloride complex at 10 mg Cd/kg treatment. With increasing Cd additions to 400 mg/kg, $Cd^{2+}$ species decreased to $40{\sim}47%$ but Cd-chloride complexes increased to $53{\sim}60$ molar %. These results demonstrated that soil contamination with heavy metals caused an adverse effect on the plant nutritional aspects of soil solution by lowering pH, increasing cations temporarily, and increasing free metal concentrations and species enough to be phytotoxic.

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Synthesis of Transition Metal Cu(II) Complexes and Their Electrochemical Properties (Cu(II) 전이금속 착물의 합성과 전기화학적 성질에 관한 연구)

  • Chae, Hee-nam;Choi, Yong-kook
    • Applied Chemistry for Engineering
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    • v.9 no.5
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    • pp.719-725
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    • 1998
  • Tridentate Schiff base ligands were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. And then Cu(II) complexes of those ligands were synthesized. The structures and properties of ligands and their complexes were studied by elemental analysis, $^1H$-NMR, IR, UV-visible spectra, and thermogravimetric analysis. The mole ratio of Schiff base to the metal of complexes was found to be 1:1. Cu(II) complexes were contemplated to be four-coordinated square planar configuration containing one water molecule. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as a supporting electrolyte was investigated by cyclic voltammetry and differential pulse voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Cu(II) complexes was quasi-reversible and diffusion-controlled as one electron by one step process Cu(II)/Cu(I). The reduction potentials of the Cu(II) complexes shifted in the positive direction in the order of [Cu(II)(HNIPC)($H_2O$)]>[Cu(II)(HNIP)($H_2O$)]>[Cu(II)(SIP)($H_2O$)]>[Cu(II)(SIPC)($H_2O$)].

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Fabrication of $Cu_xSe$ thin films by selenization of $Cu_xSe$ nanoparticles prepared by a colloidal process (CIS 태양전지용 이원 화합물 $Cu_xSe$ 나노입자를 이용한 $Cu_xSe$ 박막 제조)

  • Kim, Kyun-Hwan;Ahn, Se-Jin;Yun, Jae-Ho;Gwak, Ji-Hye;Kim, Do-Jin;Yoon, Kyung-Hoon
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.06a
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    • pp.96-98
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    • 2009
  • This report summarizes our recent efforts to produce large-grained CIGS materials from porous nanoparticle thin films. In our approach, a $Cu_xSe$ nanoparticle colloid were first prepared by reacting a mixture of CuI in pyridine with $Na_2Se$ in methanol at reduced temperature. purified colloid was sprayed onto heated molybdenum-coated sodalime glass substrates to form thin film. After thermal processing of the thin film under a selenium ambient. $Cu_xSe$ colloid and thin film were characterized by scanning electron microscopy, x-ray diffraction. The optical(direct) band gap energy of $Cu_xSe$ thin films is 1.5 eV.

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