• Journal of Korean Society of Water and Wastewater
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• v.28 no.2
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• pp.207-215
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• 2014

Wastewater containing heavy metals such as copper (Cu) and nickel (Ni) is harmful to humans and the environment due to its high toxicity. Crystallization in a fluidized bed reactor (FBR) has recently received significant attention for heavy metal removal and recovery. It is necessary to find optimum reaction conditions to enhance crystallization efficacy. In this study, the effects of crystallization reagent and pH were investigated to maximize crystallization efficacy of Cu-S and Ni-S in a FBR. CaS and $Na_2S{\cdot}9H_2O$ were used as crystallization reagent, and pH were varied in the range of 1 to 7. Additionally, each optimum crystallization condition for Cu and Ni were sequentially employed in two FBRs for their selective removal from the mixture of Cu and Ni. As major results, the crystallization of Cu was most effective in the range of pH 1-2 for both CaS and $Na_2S{\cdot}9H_2O$ reagents. At pH 1, Cu was completely removed within five minutes. Ni showed a superior reactivity with S in $Na_2S{\cdot}9H_2O$ compared to that in CaS at pH 7. When applying each optimum crystallization condition sequentially, only Cu was firstly crystallized at pH 1 with CaS, and then, in the second FBR, the residual Ni was completely removed at pH 7 with $Na_2S{\cdot}9H_2O$. Each crystal recovered from two different FBRs was mainly composed of CuxSy and NiS, respectively. Our results revealed that Cu and Ni can be selectively recovered as reusable resources from the mixture by controlling pH and choosing crystallization reagent accordingly.

• Applied Biological Chemistry
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• v.20 no.3
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• pp.300-309
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• 1977

The information related to the heavy metal pollution in the environment was obtained from studies on the effects of pH, phosphate and soil properties on the adsorption of metal ions (Cd, Cu, Ni, and Zn) by soils. Three soil materials; soil 1 with low CEC (8.2 me/100g) and low organic carbon content (0.34%); soil 2 with high CEC (36.4 me/100g) and low organic carbon content (1.8%) and soil 3 with high CEC (49.9 me/100g) and high organic carbon content (14.7%) were used. Soils were adjusted to several pH's and equilibrated with metal ion mixtures of 4 different concentrations, each having equal equivalents of each metal ion (0.63, 1.88, 3.12 and 4.38 micromoles per one gram soil with and without 10 micromoles of phosphate per one gram soil). Reported here are the results of the equilibrium study on soil I. The rest of the results on soil 2 and soil 3 will be repoted subsequeutly. Generally higher metal ion concentration solution resulted in higher final metal ion concentrations in the equilibrated solution and phosphate had minimal effect except it tended to enhance removal of cadmium and zinc from equilibrated solutions while it tended to decrease the removal of copper and nickel. In soil 1, percentages of added metal ions removed at pH 5.10 were; Cu 97, Ni 69, Cd 63, and Zn 55, while increasing pH to 6.40, they were increased to Cu 90.9, Zn 99, Ni 96, and Cd 92 per As initial metal ion concentration increased, final metal ion concentrations in the equilibrated solution showed a relationship with pH of the system as they fit to the equation $p[M^{++}]=a$ pH+b where $p[M^{++}]=-log$[metal ion concentration in Mol/liter]. The magnitude of pH and soil effects were reflected in slope (a) of the equation, and were different among metal ions and soils. Slopes (a) for metal ions in the aqueous system are all 2. In soil 1 they were; Zn 1.23, Cu 0.99, Ni 0.69 and Cd 0.59 at highest concentration. The adsorption of Cd, Ni, and Zn in soil 1 could be represented by the Iangmuir isotherm. However, construction of the Iangmuir isotherm required the correction for pH differences.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.8 no.1
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• pp.25-32
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• 2007

We investigated the silicide reaction stability between 10 nm-Col-xNix alloy films and silicon substrates with the existence of 4 nm-thick natural oxide layers. We thermally evaporated 10 nm-Col-xNix alloy films by varying $x=0.1{\sim}0.9$ on naturally oxidized single crystal and 70 nm-thick polycrystalline silicon substrates. The films structures were annealed by rapid thermal annealing (RTA) from $600^{\circ}C$ to $1100^{\circ}C$ for 40 seconds with the purpose of silicidation. After the removal of residual metallic residue with sulfuric acid, the sheet resistance, microstructure, composition, and surface roughness were investigated using a four-point probe, a field emission scanning electron microscope, a field ion bean4 an X-ray diffractometer, and an Auger electron depth profiling spectroscope, respectively, to confirm the silicide reaction. The residual stress of silicon substrate was also analyzed using a micro-Raman spectrometer We report that the silicide reaction does not occur if natural oxides are present. Metallic oxide residues may be present on a polysilicon substrate at high silicidation temperatures. Huge residual stress is possible on a single crystal silicon substrate at high temperature, and these may result in micro-pinholes. Our results imply that the natural oxide layer removal process is of importance to ensure the successful completion of the silicide process with CoNi alloy films.

• Resources Recycling
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• v.32 no.1
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• pp.21-32
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• 2023

Because the application of lithium has gradually increased for the production of lithium ion batteries (LIBs), more research studies about recycling using solvent extraction (SX) should focus on Li⁺ recovery from the waste solution obtained after the removal of the valuable metals nickel, cobalt and manganese (NCM). The raffinate obtained after the removal of NCM metal contains lithium ions and other impurities such as Na ions. In this study, we optimized a selective SX system using di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the extractant and tri-n-butyl phosphate (TBP) as a modifier in kerosene for the recovery of lithium from a waste solution containing lithium and a high concentration of sodium (Li⁺ = 0.5 ~ 1 wt%, Na⁺ = 3 ~6.5 wt%). The extraction of lithium was tested in different solvent compositions and the most effective extraction occurred in the solution composed of 20% D2EHPA + 20% TBP + and 60% kerosene. In this SX system with added NaOH for saponification, more than 95% lithium was selectively extracted in four extraction steps using an organic to aqueous ratio of 5:1 and an equilibrium pH of 4 ~ 4.5. Additionally, most of the Na⁺ (92% by weight) remained in the raffinate. The extracted lithium is stripped using 8 wt% HCl to yield pure lithium chloride with negligible Na content. The lithium chloride is subsequently treated with high purity ammonium bicarbonate to afford lithium carbonate powder. Finally the lithium carbonate is washed with an adequate amount of water to remove trace amounts of sodium resulting in highly pure lithium carbonate powder (purity > 99.2%).

• Journal of the Microelectronics and Packaging Society
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• v.19 no.1
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• pp.61-66
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• 2012

Chemical Mechanical Planarization (CMP) is a polishing process used in the microelectronic fabrication industries to achieve a globally planar wafer surface for the manufacturing of integrated circuits. Pad conditioning plays an important role in the CMP process to maintain a material removal rate (MRR) and its uniformity. For metal CMP process, highly acidic slurry containing strong oxidizer is being used. It would affect the conditioner surface which normally made of metal such as Nickel and its alloy. If conditioner surface is corroded, diamonds on the conditioner surface would be fallen out from the surface. Because of this phenomenon, not only life time of conditioners is decreased, but also more scratches are generated. To protect the conditioners from corrosion, thin organic film deposition on the metal surface is suggested without requiring current conditioner manufacturing process. To prepare the anti-corrosion film on metal conditioner surface, vapor SAM (self-assembled monolayer) and FC (Fluorocarbon) -CVD (SRN-504, Sorona, Korea) films were prepared on both nickel and nickel alloy surfaces. Vapor SAM method was used for SAM deposition using both Dodecanethiol (DT) and Perfluoroctyltrichloro silane (FOTS). FC films were prepared in different thickness of 10 nm, 50 nm and 100 nm on conditioner surfaces. Electrochemical analysis such as potentiodynamic polarization and impedance, and contact angle measurements were carried out to evaluate the coating characteristics. Impedance data was analyzed by an electrical equivalent circuit model. The observed contact angle is higher than 90o after thin film deposition, which confirms that the coatings deposited on the surfaces are densely packed. The results of potentiodynamic polarization and the impedance show that modified surfaces have better performance than bare metal surfaces which could be applied to increase the life time and reliability of conditioner during W CMP.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 1998.10a
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• pp.2-4
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• 1998

Proliferation of Nocardia amarae cells in activated sludge has often been associated with the generation of nuisance foams. Despite intense research activities in recent years to examine the causes and control of Nocardia foaming in activated sludge, the foaming continued to persist throughout the activated sludge treatment plants in United States. In addition to causing various operational problems to treatment processes, the presence of Nocardia may have secondary effects on the fate of heavy metals that are not well known. For example, for treatment plants facing more stringent metal removal requirements, potential metal removal by Nocardia cells in foaming activated sludge would be a welcome secondary effect. In contrast, with new viosolid disposal regulations in place (Code o( Federal Regulation No. 503), higher concentration of metals in biosolids from foaming activated sludge could create management problems. The goal of this research was to investigate the metal sorption property of Nocardia amarae cells grown in batch reactors and in chemostat reactors. Specific surface area and metal sorption characteristics of N. amarae cells harvested at various growth stages were compared. Three metals examined in this study were copper, cadmium and nickel. Nocardia amarae strain (SRWTP isolate) used in this study was obtained from the University of California at Berkeley. The pure culture was grown in 4L batch reactor containing mineral salt medium with sodium acetate as the sole carbon source. In order to quantify the sorption of heavy metal ions to N amarae cell surfaces, cells from the batch reactor were harvested, washed, and suspended in 30mL centrifuge tubes. Metal sorption studies were conducted at pH 7.0 and ionlc strength of 10-2M. The sorption Isotherm showed that the cells harvested from the stationary and endogenous growth phase exhibited significantly higher metal sorption capacity than the cells from the exponential phase. The sequence of preferential uptake of metals by N. amarae cells was Cu>Cd>Ni. The specific surFace area of Nocardia cells was determined by a dye adsorption method. N.amarae cells growing at ewponential phase had significantly less specific surface area than that of stationary phase, indicating that the lower metal sorption capacity of Nocardia cells growing at exponential phase may be due to the lower specific surface area. The growth conditions of Nocardia cells in continuous culture affect their cell surface properties, thereby governing the adsorption capacity of heavy metal. The comparison of dye sorption isotherms for Nocardia cells growing at various growth rates revealed that the cell surface area increased with increasing sludge age, indicating that the cell surface area is highly dependent on the steady-state growth rate. The highest specific surface area of 199m21g was obtained from N.amarae cell harvested at 0.33 day-1 of growth rate. This result suggests that growth condition not only alters the structure of Nocardia cell wall but also affects the surface area, thus yielding more binding sites of metal removal. After reaching the steady-state condition at dilution rate, metal adsorption isotherms were used to determine the equilibrium distributions of metals between aqueous and Nocardia cell surfaces. The metal sorption capacity of Nocardia biomass harvested from 0.33 day-1 of growth rate was significantly higher than that of cells harvested from 0.5- and 1-day-1 operation, indicatng that N.amarae cells with a lower growth rate have higher sorpion capacity. This result was in close agreement with the trend observed from the batch study. To evaluate the effect of Nocardia cells on the metal binding capacity of activated sludge, specific surface area and metal sorption capacity of the mixture of Nocardia pure cultures and activated sludge biomass were determined by a series of batch experiments. The higher levels of Nocardia cells in the Nocardia-activated sludge samples resulted in the higher specific surface area, explaining the higher metal sorption sites by the mixed luquor samples containing greater amounts on Nocardia cells. The effect of Nocardia cells on the metal sorption capacity of activated sludge was evaluated by spiking an activated sludge sample with various amounts of pre culture Nocardia cells. The results of the Langmuir isotherm model fitted to the metal sorption by various mixtures of Nocardia and activated sludge indicated that the mixture containing higher Nocardia levels had higher metal adsorption capacity than the mixture containing lower Nocardia levels. At Nocardia levels above 100mg/g VSS, the metal sorption capacity of activate sludge increased proportionally with the amount of Noeardia cells present in the mixed liquor, indicating that the presence of Nocardia may increase the viosorption capacity of activated sludge.

• Applied Chemistry for Engineering
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• v.27 no.1
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• pp.21-25
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• 2016

When copper alloy is used in etching process for the production of lead frame, the high concentration of heavy metals, such as iron, nickel and zinc may be included in the etching waste. Those etching waste is classified as a specified one. Therefore a customized design was designed for the purification process of the lead frame etching waste liquid containing high concentrations of heavy metals for the production of an electroplating copper(II) oxide. Since the lead frame etching waste solution contains highly concentrated heavy metal species, an ion exchange method is difficult to remove all heavy metals. In this study, a copper(I) chloride was manufactured by using water solubility difference related to the reduction-oxidation method followed by the reunion of copper(II) chloride using sodium sulfate as an oxidant. The hydrazine was chosen as a reducing agent. The optimum added amount was 1.4 mol per 1.0 mol of copper. In the case of removal of heavy metals by using the combination of reduction-oxidation and ion exchange resin methods, 4.3 ppm of $Fe^{3+}$, 2.4 ppm of $Ni^{2+}$ and 0.78 ppm of $Zn^{2+}$ can be reused as raw materials for electroplating copper(II) oxide when repeated three times.

• Clean Technology
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• v.8 no.3
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• pp.151-165
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• 2002

In the treatment of the wastewater containing metals($Cu^{2+}$, $Zn^{2+}$, $Ni^{2+}$, $Cr^{3+}$) by using batch precipitation and flocculation followed by membrane filtration, permeate flux and removal efficiency were investigated according to by the effect of pH and coagulants, and the type of membranes used and pore size. It was found that it is most effective to use $0.45{\mu}m$-polysulfone membrane and coagulant(PAC) at the conditions of the pH of 10.0~10.5 for the case of copper containing wastewater, $0.1{\mu}m$-PVDF membrane and coagulant(PAC) at the conditions of the pH of 10.0~10.5 for the case of zinc containing wastewater, $0.1{\mu}m$-PVDF membrane and coagulant at the conditions of the pH of 11.0~11.5 for the case of nickel containing wastewater, $0.2{\mu}m$ membrane and coagulant at the conditions of the pH of 8.0~8.5 for the case of chromic containing wastewater, and $0.2{\mu}m{\sim}0.45{\mu}m$ membrane and coagulant at the conditions of the pH of 11.0~11.5 for the case mixture wastewater. The permeate flux could higher as to be used coagulants except for the case of copper containing wastewater.

• Resources Recycling
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• v.16 no.6
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• pp.3-9
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• 2007

Although the ferrous material was separated by the magnetic separation before the incineration process, the municipal solid waste incineration bottom ash generated during incinerator in metropolitan area consists of many iron products which account for about $3{\sim}11%$ as well as ceramics and glasses. The formation of $NiFe_2O_4$ and $FeCr_2O_4$ with a $Fe_3O_4-Fe_2O_3$ (similar to pure Fe) on the surface of iron product was found during air-annealing in the incinerator at $1000^{\circ}C$, because Ni and Cr has a chemical attraction about iron is using to coat with Ni and Cr metals for poish or to prevent corrosion. Therefore, Fe-Ni Cr oxide can be formed on durface of the iron product and it can be separated from bottom ash through the magnetic separation. So, in this study, the separation ratio of heavy metals as magnetic separation and mineralogical formation of Fe-ion(heavy metal) in ferrous metals corroded were investigated. As the result, the separation ratio of Ni and Cr based on particle sizes accounted for about $45{\sim}50%$, and Cu and Pb accounted for below 20%. Also, the leaching concentration of Ni and Cr in bottom ash separated by magnetic separation was lower than that in fresh bottom ash.

• Journal of Soil and Groundwater Environment
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• v.9 no.4
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• pp.52-61
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• 2004

In order to remediate soils contaminated with oxyanionic As and cationic Zn and Ni through the pilot-scale acid washing, the effectiveness of acid washing and the properties of contaminated soils, fine soil particle and dissolved contaminants were evaluated. $H_{2}SO_4\;and\;H_{3}PO_4$ washing at pH $2{\sim}3$ enhanced the removal of As by the presence of competitive oxyanions and HCl washing effectively removed simultaneously As, Zn and Ni. The effectiveness of soil washing was little enhanced above the critical reaction time, and the carbonate, Fe/Mn oxide and organic/sulfides associated fraction were dominantly removed. The washing of coarse soil particles was highly efficient, but that of fine soil particles($<74{\mu}m$) was recalcitrant due to the enrichment with contaminants. Moreover, the physical separation of fine particles($<149{\mu}m$) enhanced the overall efficiency of soil washing. Therefore, both chemical extraction and separation of fine soil particles showed the high effectiveness of soil washing in the intersection point to minimize the amount of fine soil particles and to maximize the chemical extraction of contaminants.