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Structural Behavior of Mixed $LiMn_2O_4-LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ Cathode in Li-ion Cells during Electrochemical Cycling

  • Yun, Won-Seop;Lee, Sang-U
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.05a
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    • pp.5-5
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    • 2011
  • The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.

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Flexible Bronchoscopic Findings and Therapeutic Effects in Atelectasis of Children (소아 무기폐에서 굴곡성 기관지내시경 소견 및 치료적 유용성)

  • Shin, Mee Yong;Hwang, Jong Hee;Chung, Eun Hee;Moon, Jeong Hee;Lee, Ju Suk;Park, Yong Min;Ahn, Kang Mo;Lee, Sang Il
    • Clinical and Experimental Pediatrics
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    • v.45 no.9
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    • pp.1090-1096
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    • 2002
  • Purpose : We evaluated the clinical manifestations, bronchoscopic findings and therapeutic effects of flexible fiberoptic bronchoscopy in atelectasis of children. Methods : Sixty six children who received bronchoscopy due to persistent atelectasis, acute severe atelectasis and incidental atelectasis on plain chest radiography were studied retrospectively. Results : The most common causative underlying disease was pneumonia(60.4%). Other underlying conditions were pulmonary tuberculosis, chronic lung disease, postoperative state, bronchial asthma and chest trauma. The most common abnormal findings were inflammatory changes such as bronchial stenosis(n=15), mucosal edema and large amount of secretion(n=14), granulation tissue( n=3) and mucus plug(n=3) although 39.4% showed normal airways. Other findings were congenital airway anomalies, endobronchial tuberculosis, extrinsic compression and obstruction by blood clot. In 32 children with pneumonia-associated atelectasis, 43.7% revealed normal airways, and the most common abnormal findings were also inflammatory changes. Eighteen out of 39 patients who received therapeutic intervention such as suctioning of secretion, bronchial washing and intrabronchial administration of N-acetylcysteine($Mucomyst^{(R)}$) had complete or partial resolution of their atelectasis. In 32 patients with pneumonia-associated atelectasis, 56.5% showed improvement by therapeutic intervention. Conclusion : In this study, atelectasis was mainly associated with inflammatory airway diseases such as pneumonia. The most common abnormal bronchoscopic findings were inflammatory changes such as mucosal edema and large amounts of secretion and bronchial stenosis, although about 40% revealed normal airway. Flexible bronchoscopy is helpful for either diagnosis or treatment, especially in pneumonia-associated atelectasis.

Growth and Phytochemical Contents of Spinach as Affected by Different Type of Fluorescent Lamp in a Closed-type Plant Production System (밀폐형 식물 생산 시스템에서 형광등 종류에 따른 시금치의 생육 및 기능성물질 함량)

  • Kim, Hyeon Min;Kim, Hye Min;Lee, Hye Ri;Lee, Jae Eun;Hwang, Seung Jae
    • Journal of Bio-Environment Control
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    • v.26 no.4
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    • pp.386-392
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    • 2017
  • This study was conducted to examine the growth and phytochemical contents of spinach (Spinacia Oleracea L. 'Sushiro') as affected by different fluorescent lamps in a closed-type plant production system. Seeds were sown in a 128-cell plug tray filled in rockwool. The seedlings were transplanted into a DFT (deep floating technique) system with recycling nutrient solution (EC $1.5dS{\cdot}m^{-1}$ and pH 6.5) in a closed-type plant production system. The seedlings were grown under 3 types of fluorescent lamp, #S (NBFHF 32S8EX-D, CH LIGHTING Co. Ltd., China), #O (FHF32SSEX-D, Osram Co. Ltd., Germany), and #P (FLR32SS EX-D, Philips Co. Ltd., The Netherlands) at $150{\mu}mol{\cdot}m-2{\cdot}s^{-1}\;PPFD$ with a photoperiod of 14/10 (light/dark) hours. Plants were cultured under condition of $25{\pm}1^{\circ}C$ temperature and $60{\pm}10%$ relative humidity after transplanting. Thirty plants per each treatment were cultivated for $6^{th}$ week after transplanting. And growth and phytochemical contents were measured at $3^{rd}$ and $6^{th}$ week. At the $3^{rd}$ week after transplanting, the parameter values of plant height and leaf width were higher in the #O than the others. However, fresh and dry weights of root were the greatest in the #P. In addition, total phenolic concentration was the greatest in the #P. At $6^{th}$ week after transplanting, the #O had the greatest growth of spinach in the plant height and fresh and dry weights of shoot. The total phenolic contents significantly increased in the #O and showed significantly difference. However, there was no significant difference all treatments in antioxidant activity. Therefore, these results suggest that the #O was suitable for the growth and phytochemical accumulation of spinach in a closed-type plant production system.

Enhanced Graft-take Ratio and Quality of Grafted Tomato Seedlings by Controlling Temperature and Humidity Conditions (토마토 공정묘의 접목활착율과 묘소질 향상을 위한 접목 활착실내의 적정 온.습도 조건 구명)

  • Vu, Ngoc-Thang;Zhang, Cheng-Hao;Xu, Zhi-Hao;Kim, Young-Shik;Kang, Ho-Min;Kim, Il-Soep
    • Journal of Bio-Environment Control
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    • v.22 no.2
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    • pp.146-153
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    • 2013
  • This study was conducted to enhance graft-take ratio and quality of grafted tomato seedlings by controlling temperature and humidity during the healing and acclimatization processes. Three temperature levels ($20^{\circ}C$, $23^{\circ}C$, and $26^{\circ}C$) were carried out to determine optimum temperature on four rootstocks. In addition, twelve combinations of three relative humidity levels (70%, 80%, and 90%) and four temperature levels ($17^{\circ}C$, $20^{\circ}C$, $23^{\circ}C$, and $26^{\circ}C$) were set up to evaluate the effect of relative humidity and temperature on the graft-take ratio of grafted seedlings. In the other hand, five relative humidity periods (H0, H1, H2, H3, and H4: 90% relative humidity for first 0, 1, 2, 3 and 10 days and afterwards relative humidity was reduced to 70%, respectively) were examined effect of relative humidity periods on the graft-take and quality of grafted seedlings. The higher graft-take ratios (84.0~87.4%) were showed at $23^{\circ}C$ compared to $20^{\circ}C$ and $26^{\circ}C$ in all rootstocks. Graft-take ratios decreased and number of diseased plants increased at high temperature. The graft-take ratios increased with increasing relative humidity in all temperature levels on the $3^{rd}$ and $7^{th}$ day after grafting. However, increasing relative humidity significantly increased percent of diseased plants. The graft-take ratio reduced at ($26^{\circ}C$) and ($17^{\circ}C$) temperature under all relative humidity conditions. The graft-take ratio increased with increasing period of 90% relative humidity. Maximum graft-take ratios were observed in H2 and H3 treatments. Graft-take ratio decreased with increasing 90% relative humidity for 10 days (H4). Diseased plants had not been found in H0, H1, H2, and H3 treatments. Seedling quality was improved through increasing fresh and dry weight of root, compactness, and root morphology of tomato seedlings in H2 and H3 treatments. Therefore, high relative humidity (90%) for first 2 or 3 days and afterwards reduced low relative humidity (70%) at $23^{\circ}C$ condition during healing and acclimatization promoted the graft-take and quality of grafted tomato seedlings.

Improvement of Tomato Seedling Quality under Low Temperature by Application of Silicate Fertilizer (저온 저장 시 규산 처리에 의한 토마토 묘소질 향상)

  • Vu, Ngoc-Thang;Tran, Anh-Tuan;Le, Thi-Tuyet-Cham;Na, Jong-Kuk;Kim, Si-Hong;Park, Jong-Man;Jang, Dong-Cheol;Kim, Il-Seop
    • Journal of Bio-Environment Control
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    • v.26 no.3
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    • pp.158-166
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    • 2017
  • The object of this study was to improve tomato seedling quality in low temperature(below 7, $10^{\circ}C$ during night time or daily mean air temperature was $18^{\circ}C$) by application of silicate fertilizer. Six different silicate fertilizer concentrations (8, 16, 32, 64, 128, and 256mM) or water as the control were applied to tomato seedlings twice a week for 20 days. Positive effects were observed in the growth parameters of the seedlings treated with 16 and 32mM silicate fertilizer; the most effective concentration of silicate at which seedlings showed the best performance was 16mM. However, a high concentration of silicate (256mM) caused negative effects on the growth. The transpiration rate decreased alongside with the increase of silicate concentration up to 32mM, possibly due to the increased stomatal diffusive resistance. Silicate stimulated the growth and development of tomato seedlings, resulting in increased growth parameters and root morphology. However, no significant differences were observed among treatment numbers of soil-drenching wuth the silicate (6, 10, or 20 times with 16mM) for 20 days, suggesting that silicate treatment with 6 times may be sufficient to induce the silicate effects. The application of 16mM of silicate fertilizer reduced relative ion leakage and chilling injury during low temperature storage. In addition, the seedlings treated with silicate fertilizer recovered faster than those without silicate treatment after low temperature storage.

Biological treatment process for Food wastewater Using ER-1 bioreactor (다단 수직형 호기성반응기(ER-1)를 이용한 음식물 폐수의 생물학적 처리기술)

  • Lee, Jae-ki;Choi, Hong-Bok;Shin, Eung-Bai;Park, Ju-Hyoung;Choi, Eun-Ju;Kim, Jung-Rae;Park, Young-Sook
    • Journal of the Korea Organic Resources Recycling Association
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    • v.14 no.4
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    • pp.113-120
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    • 2006
  • Wastewater generated through the food waste recycling process have known high concentration, BOD 20,000~150,000 mg/L, which has to treat to the proper level because of a ban on reclamation. But it is impossible to treat less than 10 days by existing water treatment plant. Ecodays Ltd. is to treat this wastewater during 2~4 days by ER-1, which can simultaneously induce the modified PFR(Plug Flow Reactor) of the oxygen transfer rate, MLVSS concentration, and influent concentration to top from bottom of reactor. We tested the pilot test about low concentration food wastewater(BOD 16,500 mg/L) and high concentration food wastewater(64,431 mg/L) at the food waste recycling plant of H-Gun(20t/d). Hydraulic retention time(HRT) of ER-1 for low concentration food wastewater is 2.5day. In low concentration conditions, ER-1 treatment efficiency is to appear BOD 99%, COD 98%, TN 97%, and TP 96%. While ER-1 process for high concentration food wastewater treatment is composed 2 stages, which are to be HRT 2.5day for law wastewater and HRT 1.5 day for secondary treatment. In high concentration conditions, ER-1 treatment efficiency is to appear BOD 97%, COD 84%, TN 66%, and TP 95%. It is treated without temperature control about high temperature($50^{\circ}C$) to appear low treatment efficiency in high concentration conditions.

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Quality Change during Harvest Time and Storage of Various Cabbages Grown on High Land by Different Transplanting Times (정식시기에 따른 고랭지 양배추의 수확 및 저장중 품질변화)

  • Eum, Hyang-Lan;Lee, Young-Hoon;Hong, Sae-Jin;Shin, Il-Sheob;Yeoung, Young-Rok
    • Journal of Bio-Environment Control
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    • v.21 no.2
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    • pp.95-101
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    • 2012
  • This study was conducted to investigate the effect of climate conditions during cultivation and harvesting on the quality and storability of fresh bulb cabbage (Brassica oleracea L. var. capitata). Plug seedlings of six cabbage cultivars were transplanted to Gangneung-Wonju University high elevation research station in Gangwon province (780 m above sea level, lat. $37.5^{\circ}N$.) and harvested with four different harvest times like August 3 ($1^{st}$), August 13 ($2^{nd}$), August 23 ($3^{rd}$), and September 10 ($4^{th}$), respectively from 50 days after transplanting. Weight loss, Hunter color factors, firmness, and soluble solids content (SSC) of the cabbage bulbs were investigated during storage at $3^{\circ}C$ (85% RH) and $25^{\circ}C$ (60% RH). Decreased bulb weight and poor quality cabbages were apparent at the late transplanting (July 14) and harvest (September 10) respectively. Quality index such as firmness and SSC at August 23 ($3^{rd}$) harvested cabbage was better than August 3 ($1^{st}$) and August 13 ($2^{nd}$) cabbages due to the good weather condition just before harvesting. The cv. 'Speed king' and 'Minix 40' showed good qualities among the cultivars, especially when the bulbs were harvested during sunny day conditions from one week before harvesting. Also SSC was influenced by weather condition before harvesting rather than transplanting date, while firmness was influenced by transplanting and harvest date. However, the differences among the cultivars were not significant. The potential of storage as maintaining the quality was different, depending on weather conditions at harvest time. Generally the storage periods of six cultivars were around 3~5 days and 9~10 days at room and low temperature, respectively. However, the August 3 ($1^{st}$) harvested cabbage lost their marketable quality very fast because of rainy and cloudy weather condition before harvesting and also storability of bulbs was 2 days and 4 days at room temperature and $3^{\circ}C$, respectively. Quality index was also not significant difference among cultivars.

Growth Characteristics of Lettuce under Different Frequency of Pulse Lighting and RGB Ratio of LEDs (LED의 간헐조명과 RGB 비율에 따른 상추의 품종별 생육 특성)

  • Kim, Sungjin;Bok, Gwonjeong;Lee, Gongin;Park, Jongseok
    • Journal of Bio-Environment Control
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    • v.26 no.2
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    • pp.123-132
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    • 2017
  • This study was aimed to investigate the effect of 1)irradiation with several different ratios using red, green, and blue LEDs and 2)various pulsed light irradiation with 50% duty ratio using red and blue LEDs on the growth and morphogenesis of three lettuce cultivars (Lactuca sativar L. cv. 'Jukchukmeon', 'Lolo Rosa', and 'Grand Rapid') in hydroponics culture system for 4 weeks after transplanting. Seeds were sown in rock-wool plug trays and they were placed in a culture room which was controlled at $23{\pm}1^{\circ}C/18{\pm}1^{\circ}C$ temperature and 50-60/70-85% for day and night, respectively, during cultivation period. Irradiated RGB ratios with LEDs were 6:3:1, 5:2.5:2.5, 3:3:4, 2:2:6, and 1:1:8 with $110{\pm}3{\mu}mol{\cdot}m^{-2}{\cdot}s^{-1}$ PPFD on the surface of cultivation bed. The frequencies of pulsed lighting was 50, 100, 500, 1,000, 5,000, 10,000, 25,000Hz (20, 10, 0.1, 0.04 ms) with red and blue LEDs and 50% duty ratio. At the RGB ratio of 6:3:1, the average fresh weight of 'Jukchukmeon' was significantly higher than that of other RGB treatments, but no significant difference compared to the fluorescent treatment. The average fresh weight at 1:1:8 RGB ratio in 'Lolo Rosa' was significantly lower than that of other RGB treatments. Leaf number and fresh weight of 'Grand Rapid' were significantly lower in the control and 1:1:8 RGB treatments, compared to the other RGB treatments. As the ratio of blue light increased, leaf length decreased and leaf shape became round in three lettuces. Although there is little change in growth, it could not be found any tendency to affect the growth and morphogenesis of three lettuces caused by increasing or decreasing frequency of pulsed lighting with 50% duty ratio at the $72{\mu}mol{\cdot}m^{-2}{\cdot}s^{-1}$ PPFD.

Design and Optimization of Pilot-Scale Bunsen Process in Sulfur-Iodine (SI) Cycle for Hydrogen Production (수소 생산을 위한 Sulfur-Iodine Cycle 분젠반응의 Pilot-Scale 공정 모델 개발 및 공정 최적화)

  • Park, Junkyu;Nam, KiJeon;Heo, SungKu;Lee, Jonggyu;Lee, In-Beum;Yoo, ChangKyoo
    • Korean Chemical Engineering Research
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    • v.58 no.2
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    • pp.235-247
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    • 2020
  • Simulation study and validation on 50 L/hr pilot-scale Bunsen process was carried out in order to investigate thermodynamics parameters, suitable reactor type, separator configuration, and the optimal conditions of reactors and separation. Sulfur-Iodine is thermochemical process using iodine and sulfur compounds for producing hydrogen from decomposition of water as net reaction. Understanding in phase separation and reaction of Bunsen Process is crucial since Bunsen Process acts as an intermediate process among three reactions. Electrolyte Non-Random Two-Liquid model is implemented in simulation as thermodynamic model. The simulation results are validated with the thermodynamic parameters and the 50 L/hr pilot-scale experimental data. The SO2 conversions of PFR and CSTR were compared as varying the temperature and reactor volume in order to investigate suitable type of reactor. Impurities in H2SO4 phase and HIX phase were investigated for 3-phase separator (vapor-liquid-liquid) and two 2-phase separators (vapor-liquid & liquid-liquid) in order to select separation configuration with better performance. The process optimization on reactor and phase separator is carried out to find the operating conditions and feed conditions that can reach the maximum SO2 conversion and the minimum H2SO4 impurities in HIX phase. For reactor optimization, the maximum 98% SO2 conversion was obtained with fixed iodine and water inlet flow rate when the diameter and length of PFR reactor are 0.20 m and 7.6m. Inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO2 conversion with fixed temperature and PFR size (diameter: 3/8", length:3 m). When temperature (121℃) and PFR size (diameter: 0.2, length:7.6 m) are applied to the feed composition optimization, inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO2 conversion.

Effects of Selenium Supplying Methods on the Growth and Se Uptake of Hydroponically Grown Tomato Plants (Selenium공급방법이 수경재배 토마토의 생장과 Se 흡수에 미치는 영향)

  • Lee Cheol-Kyu;Cho Kyung-Cheol;Lee Jeong-Hyun;Cho Ja-Yong;Seo Beom-Seok;Yang Won-Mo
    • Journal of Bio-Environment Control
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    • v.14 no.4
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    • pp.284-288
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    • 2005
  • This study was conducted to clarify the effects of supplying methods of selenium on the growth and Se uptake of hydroponically grown tomato plants. Tomato seeds (Lycopersicum esculentum Mill. cv. Momotaro T-93, Daki Seed Co.) were sown in plug tray with fifty holes, and raised for sixty days. Tomato seedlings transplanted to coco fiber slabs were supplied with the nutrient solutions adjusted to EC $2.3dS{\cdot}m^{-1}$ and pH $5.8\~6.2$ recommended by the Japanese Horticultural Experiment Station. Selenium forms used were inorganic $SeO_2$ (here in after referred to Se) and organic selenium chlenium with sugar fatty acid ester (here in after referred to chelated-Se). 10 ppm selenium solutions were treated to tomato plants with foliar applications, drenching, and foliar application plus drenching. Growth characteristics in terms of plant height, number of leaves, leaf area and chlorophyll content were significantly increased in the plot of foliar application ot Se, and in the plot of foliar application plus drenching of chelated-Se than other plots, respectively. Transported contents of selenium into the tomato fruits were highest as 0.302 ppm in the plot of foliar application plus drenching of chelated-Se. Also, it had tended to be higher in the plot of foliar application plus drenching than in the plots of foliar application or drenching in both of Se and chelated-Se. Foliar application and drenching of organic chelated-Se were effective to produce the functional tomato fruits.