• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2011.05a
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• pp.47-48
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• 2011

The effect of solution acidity and organic additives, polyethylene glycol (PEG), on the trivalent chromium electroplating was systematically investigated in the view point of solution stability, electroreduction of trivalent chromium ions and characterization of deposition layer. It was found that, the concentration of fraction chromium complexes in the trivalent chromium bath containing formic acid is strongly depended on pH value. PEG molecules were stable in trivalent chromium bath containing formic acid via studies on electrospray ionization mass spectrometry (ESI-MS) and UV-Vis. However, the presence of PEG molecules decreased the reductive current of hydrogen evolution, increasing of current efficiency higher about 10 % compared with solutions without PEG. Moreover, 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 a low speed. In this study, the effect of solution acidity was emphasized important, there, it controlled the formation of complexes in the solution, cathodic film (CF) during deposition, and properties of deposited layer. By electrochemical quartz crystal microbalance (EQCM), studies show that chromium electrodeposition occurs via the formation of intermediate complexes and adsorption on the cathode surface, which hinder the penetration of ions from bulk solution to the cathode surface.

• 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.

• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.790-793
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• 1996

The azacrown compound, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N"-tri(methyl-acetic acid)(N3O2-tri(methylacetic acid)) was synthesized by modified procedure of Krespan. Potentiometric method has been used to determine the protonation constants of N3O2-tri(methylacetic acid) and stability constants of complexes on the divalent transition metal ions (Co2+, Ni2+, Cu2+, and Zn2+) and trivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with N3O2-tri(methylacetic acid). The stability constants for the complexes of the divalent transition metal ions studied in the present work with N3O2-tri(methylacetic acid) were 11.4 for Co2+, 11.63 for Ni2+, 13.51 for Cu2+, and 11.65 for Zn2+, respectively. Thus, the order of the stability constants for complexes on the transition metal ions with N3O2-tri(methylacetic acid) was shown Co2+ < Ni2+ < Cu2+ > Zn2+ as same as the order of Irving-Williams series. The stability constants of Ce3+, Eu3+, Gd3+, and Yb3+ trivalent lanthanide metal ion complexes of N3O2-tri(methylacetic acid) were, respectively, 11.26 for Ce3+, 11.56 for Eu3+, 11.49 for Gd3+, and 11.80 for Yb3+. The values of the stability constants on trivalent metal ions with the ligand are increasing according to increase atomic number, due to increase acidity. But the value of stability constant of Gd3+ ion is less than the value of Eu3+ ion. This disordered behavior is also reported by Moeller.

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1158-1161
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• 1997

The potentiometric methods have been used to determined the protonation constants (logKiH) for the synthesized 1,7,13-trioxa-4,10,16-triazacyclooctadecane-N,N',N''-tri(methylacetic acid) [N3O3-tri(methylacetic acid)] and the stability constants (logKML) of the complexes of divalent and trivalent metal ions with the ligand N3O3-tri(methylacetic acid). The protonation constants of N3O3-tri(methylacetic acid) were 9.70 for logK1H, 9.18 for logK2H, 7.27 for logK3H, 3.38 for logK4H, and 2.94 for logK5H. The stability constants for the complexes of divalent metal ions with N3O3-tri(methylacetic acid) were 10.39 for Co2+, 10.68 for Ni2+, 13.45 for Cu2+, and 13.00 for Zn2+. The order of the stability constants for the complexes of the divalent metal ions with N3O3-tri(methylacetic acid) was Co2+ < Ni2+ < Zn2+ < Cu2+. The stability constants for the complexes of trivalent metal ions with N3O3-tri(methylacetic acid) were 16.20 for Ce3+, 16.40 for Eu3+, 16.27 for Gd3+, and 15.80 for Yb3+. The results obtained in this study were compared to those obtained for similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N"-tri(methylacetic acid) and 1,7,13-trioxa-4,10,16-triazacyclooctadecane-N,N',N"-triacetic acid, which have been previously reported.

• Membrane Journal
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• v.12 no.1
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• pp.51-53
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• 2002

The hydrogen ions in poly (vinyl alcohol) (PVA)/sulfosuccinic acid (SSA) membranes substiuted with $Li^+, Na^+, and K^+/ $of monvoalent metal ions, $Mg^{2+}, Ca^{2+} and Ba^{2+}$ of divalent metal ions, and $Al^{3+}$ of trivalent metal ion. In addition, $Li^+ ions were exchanged with varing reaction time. The effects of metal ions exchanged were investigated in terms of methanol permeability -uling diffusion cell. The methanol permeabilies decreased in the sequence of $Na^+, Li^+ and K^+$ and this might be due to the 'Salting-out' effect while the methanol permeabilities for divalent and trivalent ion-substituted membranes were affected by the combined effects of salting-out, eletrostatic crosslinking and extent of metal ion substiution. As for $Li^+$ ions, methanol permeabilities of PVA/SSA membranes decreased in proportion to the degrees of subsituted $Li^+$ ions.

• Journal of the Korean institute of surface engineering
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• v.37 no.3
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• pp.179-184
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• 2004

Hard chromium coating technology using hexavalent chromium bath is widely used in various industries. Because of the serious health and environmental problems of hexavalent chromium, many attempts to alternate the hexavalent chromium plating have been made over 50 years. Trivalent chromium plating is one of the challengeable technologies to alternate hexavalent chromium plating. It is relatively none-toxic. Although some papers have described hard chromium coatings produced from trivalent chromium solution, it has limited the industrialization because of chemical and electrochemical problems of trivalent chromium ions. This paper introduces a number of factors for successful trivalent chromium plating, to give a some information about trivalent chromium process.

• Journal of the Korean institute of surface engineering
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• v.44 no.1
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• pp.7-12
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• 2011

The effect of organic additives, polyethylene glycol (PEG), on the trivalent chromium electroplating was analysed in the view point of current efficiency, solution stability and metallurgical structure. It was measured that PEG-containing trivalent chromium solution had about 10% higher current efficiency than pure solution and controlled the micro-crack density of electrodeposits. PEG exhibited profound effect on the solution stability by reducing the consumption rate of formic acid which acts as a complexant to lower the activation energy required for electrochemical reduction of trivalent chromium ions. It was also revealed that the formation of chromium carbide layer was facilitated in the presence of polyethylene glycol, which meant easier electrochemical codeposition of chromium and carbon, not single chromium deposition. Trivalent chromium layer formed from PEG-containing solution was amorphous with local nano-crystalline particles, which were prominently developed on the entire surface after non-oxidative heat treatment.

• Bulletin of the Korean Chemical Society
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• v.17 no.4
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• pp.398-401
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• 1996

• Bulletin of the Korean Chemical Society
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• v.22 no.6
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• pp.641-643
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• 2001

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.170.2-170.2
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• 2015

Enormous interest in trivalent rare-earth (RE) ions activated luminescent materials has been gaining owing to their promising applications in bio-imaging, solar cells, white light-emitting diodes and field-emission displays. Among these trivalent RE ions, dysprosium (Dy3+) was widely investigated due to its unique photoluminescence (PL) emissions. A series of Dy3+-activated CaWO4 phosphors were prepared by a facile high-temperature solid-state reaction method. The X-ray diffraction, PL spectra, cathodoluminescence (CL) spectra as well as PL decay curves were used to characterize the prepared samples. Under ultraviolet light excitation, the characteristic emissions of Dy3+ ions were observed in all the obtained phosphors. Furthermore, the PL emission intensity increased gradually with the increment of Dy3+ ion concentration, reaching its maximum value at an optimized Dy3+ ion concentration. Additionally, color-tunable emissions were obtained in Dy3+-activated CaWO4 system by adjusting the Dy3+ ion concentration and excitation wavelength. Ultimately, strong CL properties were observed in Dy3+-activted CaWO4 phosphors. These results suggested that the Dy3+-activted CaWO4 phosphors may have potential applications in the field of miniature color displays.