• Journal of Institute of Control, Robotics and Systems
• /
• v.19 no.10
• /
• pp.891-895
• /
• 2013

This paper proposes the development of a new method for online analysis which measured acid concentration in a pickling line. Pickling is the most important step to remove surface scale layers and is strongly depending on the exactly controlled pickling liquor composition. Today, there is no feasible system available for the online control of pickling lines. Within this paper, new methods for online analysis of pickling liquors have been tested and implemented into an overall pickling process control tool. This method measured simultaneously the hydrochloric acid and iron ion concentration in a solution of hydrochloric acid by measuring the ultrasonic speed, the solution temperature, and the electrical conductivity. Experimental results showed excellent precision and the measurement error was ${\pm}2g/l$ compared with the neutralization titration measurement.

• Clean Technology
• /
• v.11 no.1
• /
• pp.21-28
• /
• 2005

Nitric acid free pickling solution was applied to solve the severe environmental problems attributed to nitric acid during pickling process of stainless steel product. In points of pickling capability and erosion of stainless steel base metal, a solution contains I% of hydrochloric acid and 2% of hydrofluoric acid and hydrogen peroxide was revealed as the best alternative to conventional mixed acid of nitric acid and hydrofluoric acid. To keep the pickling capability, it was necessary to maintain the concentration ratio of hydrogen peroxide to hydrochloric acid above 0.5.

• Resources Recycling
• /
• v.26 no.5
• /
• pp.97-104
• /
• 2017

Nuclear fuel cladding tubes are manufactured through pilgering and the annealing process. In order to remove the oxidized layer and impurities on the surface of the tube, a pickling process is required. Zirconium (Zr) is dissolved in a HF and $HNO_3$ acid mixture during the process and the pickling waste acid, including the dissolved Zr, is completely discarded after neutralization. This study observes the effects of the residual impurities (Ba) in the pickling solution regenerated from the $BaF_2$ precipitation process on the waste pickling solution. In addition, the concentration of Ba and Zr for the actual nuclear fuel cladding tube process was optimized. The regenerated pickling solution was tested through a pilot plant pickling process device that simulates the commercial pickling process of nuclear fuel cladding tubes, and the pickling efficiency was analyzed through AFM analysis of the roughness of the cladding tube surface.

• Korean Chemical Engineering Research
• /
• v.55 no.6
• /
• pp.785-790
• /
• 2017

To collect zinc, Fe and Zn in spent pickling solution were extracted by using TBP (tributyl phosphate), and Zn was recovered from extracted solution to zinc oxalate particles by oxalic acid solution. The reusability of TBP solvent was also tested. The distribution coefficient of Zn was not affected by the concentration of Fe in spent pickling solution, almost constant with the values of 7.12~9.31 when extracted by TBP solvent. It was found that the extraction capacity of TBP solvent for Zn is higher than that for Fe. The extraction efficiency of Zn was higher than 95%, while most of Fe was left in aqueous phase. After the recovery, the used TBP solvent could be repeatedly reused for the extraction of Zn up to eight times. XRD analysis showed that zinc oxalate ($ZnC_2O_4$ $2H_2O$) was formed from the reaction of Zn-TBP and oxalic acid. From the results of SEM analysis, the formation of zinc oxalate particle was strongly affected by the concentration of oxalic acid. In summary, Zn in spent pickling solution was successfully separated and recovered with TBP solvent and oxalic acid solution, respectively.

• Korean Journal of Materials Research
• /
• v.29 no.8
• /
• pp.483-490
• /
• 2019

Currently, the Korean nuclear industry uses ZIRLO as material for nuclear fuel cladding(zirconium alloy). KEPCO Nuclear Fuel is in the process of developing a HANA alloy to enable domestic production of cladding. Cladding manufacture involves multistage heat treatments and pickling processes, the latter of which is vital for the removal of defects and impurities on the cladding surface. SMUT that forms on the cladding surface during such pickling process is a source of surface defects during heat treatment and post-treatment processes if not removed. This study analyzes ZIRLO, HANA-4, and HANA-6 alloy claddings to extensively study the SEM/EDS, XRD, and particle size characteristics of SMUT, which are second phase particles that are formed on the cladding surface during pickling processes. Using the analysis results, this study observes SMUT formation characteristics according to Nb concentration in Zr alloys during the washing process following the pickling process. In addition, this study observes SMUT removal characteristics on cladding surfaces according to concentrations of nitric acid and hydrofluoric acid in the acid solution.

• Korean Journal of Materials Research
• /
• v.27 no.12
• /
• pp.672-678
• /
• 2017

In the production of zirconium cladding tube, a pickling acid solution is used to remove surface contaminants, which generates tons of pickling acid waste. The waste pickling solution is a valuable resource of Hf-free Zr. Many studies have investigated separating the Hf-free Zr source from the waste pickling acid. The results showed that $Ba_2ZrF_8$ precipitates prepared from the waste pickling acid were useful as an electrolyte for the electrorefining of Zr in molten salt. In the present work, electrorefining was performed in a $Ba_2ZrF_8-LiF$ binary electrolyte to recover Zr from a Hf-free CuZr ingot anode prepared by electroreduction. Before electrorefining, two pretreatments are performed. First, electrolyte melting was carried out to determine the eutectic temperature, and second, the electrolyte was treated to eliminate impurities, mainly hydride. After electrorefining, the cathode deposits were analyzed by $O_2$ gas analyzer and SEM-EDX to explore the possibility of recovering nuclear-grade Zr metal. Moreover, the anode was analyzed by SEM-EDX to determine the Zr dissolution depth.

• Corrosion Science and Technology
• /
• v.2 no.5
• /
• pp.233-237
• /
• 2003

Pickling inhibitors can be used to form an adsorbed layer on the metal surface to hinder the discharge of H^+$ and dissolution of metal ions. Nitrogen-containing inhibitors were selected as corrosion inhibitors for mild steel (MS) in pickling acid process. In this study, the addition of inhibitor, the pickling temperatures and the pickling times were the parameters to investigate the effects on the inhibition efficiency (IE) for MS by using weight loss measurement. Preliminary results show that the IE increased with the increase in pickling time from 10 minutes to 60 minutes, and the IE also increased with the increase in temperature at room temperature and $40^{\circ}C$. At the higher temperature. the IE values are higher and almost independent with the pickling time. Furthermore, the potentiodynamic polarization, open circuit corrosion potential-time and corrosion current-time studies show that nitorgen-containing inhibitor behaves predominantly as cathodic polarization. The roughness test and SEM investigation are also studied in this paper.

• Journal of Institute of Control, Robotics and Systems
• /
• v.21 no.12
• /
• pp.1173-1177
• /
• 2015

This paper deals with estimating the acid concentration of pickling process using the Volterra inputs. To estimate the acid concentration, the whole pickling process is represented by the grey box model consists of the white box dealing with known system and the black box dealing with unknown system. Because there is a possibility of nonlinear term in the unknown system, the Volterra series are used to estimate the acid concentration. For the white box modeling, the acid tank solution level and concentration equations are used, and for the black box modeling, the acid concentration is estimated using the Volterra Least Mean Squares (LMS) algorithm and Least Squares (LS) algorithm. The LMS algorithm has the advantage of the simple structure and the low computation, and the LS algorithm has the advantage of lowest error. The simulation results compared to the measured data are included.

• The Korean Journal of Food And Nutrition
• /
• v.19 no.4
• /
• pp.398-409
• /
• 2006

Changes of component(amino acid, free sugar, fatty acid and mineral) and antioxidant effect by pickling of soybeans we.e investigated. Soybean cultivars, Daewon, Pungsannamul, Hwaeum(yellow bean), Ilpum Black and Zynuni(black bean) were soaked in persimmon vinegar for 10 days at $20^{\circ}C$. The major amino acids of raw soybeans were glutamic acid, aspartic acid, lysine and leucine. The content of total amino acid decreased by pickling. The major free sugar of raw soybeans were glucose, fructose and sucrose. Sucrose decreased and glucose and fructose increased by pickling. Maltose was found only in pickled Daewon and Ilpum Black. Linoleic and linolenic acid content of raw soybeans were $49.3%{\sim}57.1%\;and\;7.8{\sim}8.9%$, and the fatty acid contents did not change by pickling. The major mineral elements were K, P and Mg, and their compositions except for Na did not change by pickling. Total phenolic compound, vitamin $B_1$ and C content increased during pickling. The antioxidant effects, electron donating abilities, nitrite-scavenging abilities increased by pickling.

• Journal of the Korean institute of surface engineering
• /
• v.49 no.1
• /
• pp.62-68
• /
• 2016

A chromium-free Ce-based conversion coating formed by immersion in a solution containing cerium chloride and nitric acid on AZ31 magnesium alloy has been studied. The effects of acid pickling on the morphology and the corrosion resistance of the cerium conversion coating were investigated. The corrosion resistance of the conversion coating prepared on AZ31 Mg alloy after organic acid pickling was better than that of inorganic acid pickling. The morphology of the conversion-coated layer was observed using optical microscope and SEM. Results show that the conversion coatings are relatively uniform and continuous, with thickness 1.0 to $1.1{\mu}m$. The main elements of the conversion coating of AZ31 Mg alloy are Mg, O, Al, Ce and Zn by EDS analysis. The electrochemical polarization results showed that the Ce-based conversion coating could reduce the corrosion activity of the AZ31 Mg alloy substrates in the presence of chloride ions.