• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2017.05a
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• pp.165-165
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• 2017

지난 수 십 년 동안, 전 세계적으로 자원의 소비가 급격히 증가하게 되면서 최근 자원 고갈은 물론 환경오염이 커다란 이슈로 문제가 되고 있다. 이에 따라 재료 관련 분야에 있어서는 보다 효율적이고 친환경적인 방법으로 자원을 활용해야 된다는 필요성이 대두되었고 이와 같은 관점에서 목적하는 성분이 우수하고 환경 친화적인 표면처리 재료 개발연구가 활발하게 진행되고 있는 실정이다. 그 중 플라즈마 전해 산화(Plasma Electrolytic Oxidation, PEO)는 알루미늄, 마그네슘 등의 경금속의 경도를 향상시키고 높은 내마모성, 내식성을 갖게 하는 표면처리로써 그 관심이 증가하고 있다. 이 플라즈마 전해 산화는 일반적으로 공정비용 대비 효과적이고 환경 친화적이며 코팅 성능 면에서 우수하다고 알려져 있다. 이러한 고유한 특성으로 인해 플라즈마 전해 산화 코팅은 최근 몇 년 동안 기계, 자동차, 우주항공, 의학 및 전기 산업 등의 분야에서 그 적용이 점차 증가하고 있는 상황이다. 한편, 플라즈마 전해 산화 코팅을 하는 모재들의 경우 부동태 산화피막을 용이하게 형성할 수 있는 특성의 모재에 한정되고 있어서 그 응용확대에 한계가 있는 것이 사실이다. 따라서 본 연구에서는 플라즈마 전해 산화법을 사용하여 용융알루미늄도금 강판 상에 산화피막 형성을 시도하였다. 전원공급 장치의 양극은 전해질 속에 잠겨있는 작동전극에 연결하고 음극은 대전극 역할을 하는 스테인레스강 전해질 용기에 연결되었다. 전해질은 Sodium Aluminate 및 기타 첨가제를 함유한 것을 사용하였고 온도는 열교환기를 사용하여 $30^{\circ}C$ 이하로 유지되었다. 또한 여기서 전류밀도는 $5{\sim}10A/dm^2$, 실험 주파수는 700Hz, Duty cycle은 30 및 90%의 각 조건에서 공정처리 시간을 각각 30분 및 60분 동안 진행하였다. 이와 같은 조건에서 형성한 막들에 대해서는 주사형전자현미경(SEM)을 이용하여 코팅 막의 표면 및 단면의 모폴로지를 관찰하였음은 물론 EDS 및 XRD 측정을 통하여 원소조성분포 및 결정구조를 각각 분석하였다. 또한 이 코팅 막들에 대한 내식성은 5% 염수분무 환경 중 노출시험(Salt spray test), 3% NaCl 용액에서의 침지 시험 및 전기화학적 동전위 양극분극(Potentiodynamic Polarization) 시험을 진행하여 평가하였다. 이상의 실험결과에 의하면, 제작조건별 플라즈마 전해 산화 코팅 막의 모폴로지 및 결정구조가 상이하게 나타나는 것을 알 수 있었다. 코팅 막의 모폴로지 관찰 결과, 공정 시간에 비례하여 표면에 존재하는 원형 기공의 수는 감소하였으나 그 크기가 커지고 크레이터의 직경 또한 커진 것이 확인되었다. 이 기공은 마이크로 방전에 의해 형성된다고 알려져 있는데 공정 시간이 증가함에 따라 코팅 두께가 점차 증가하여 마이크로 방전의 빈도수가 줄어들고 그 강도는 증가하게 되어 기공 크기가 증가한 것으로 사료된다. 또한 공정시간이 긴 시편에서 표면에 크랙이 다수 존재하는 것으로 확인되었다. 이것은 방전에 의해 고온이 된 소재가 차가운 전해질과 만나게 되어 생긴 큰 온도구배로 인해 강한 열응력이 발생하여 균열을 초래한 것으로 보인다. 조성원소 분석 결과 원형 기공 주변의 크레이터 영역에는 알루미늄이 풍부하였으며 그 주변에 결절상을 갖는 구조에서는 전해질 성분의 원소가 포함되어 있는 것이 확인되었다. 이러한 코팅 막의 표면 특성은 내식성에 영향을 주게 된 원인으로 사료된다. 동전위 분극측정 결과에 의하면 플라즈마 전해 산화 공정 시간이 길어질수록 부식전류밀도가 증가하였다. 이것은 공정시간이 길어짐에 따라 강한 방전이 발생하여 기공의 크기가 증가하고 크랙이 발생하게 되면서 내식성이 저하된 것으로 판단된다. 종합적으로 재료특성 분석 및 내식성 평가를 분석한 결과, 플라즈마 전해 산화의 공정 시간이 너무 길게 되면 오히려 내식성은 저하되는 것이 확인되었다. 이상의 연구를 통하여 고내식 특성을 갖는 플라즈마 전해 산화 막의 유효성을 확인하였으며 용융알루미늄강판 상에 실시한 플라즈마 전해 산화 처리에 대한 기초적인 응용 지침을 제시할 수 있을 것으로 사료된다.

• Journal of Conservation Science
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• v.26 no.2
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• pp.171-182
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• 2010

The slag excavated from Gyesil-ri in Gongju, Yeonje-ri in Cheongwon and Beopcheonsaji (temple) site in Wonju are analyzed by X-ray Fluorescence Analyzer, metallurgical microscope, SEM-EDS etc., for chemical composition and microstructure to figure out the raw material and the iron manufacturing technique. First of all, as a result of principal component analysis, the total Fe-content of slag from Gyesil-ri is 39 to 44% and the modified rate is 15 to 21%, which is common in ancient iron slag. Yeonje-ri site is found the ancient iron-smelting furnace. The total Fe-content of slag from Yeonje-ri is 41 to 43% and modified rate is 18~30%, which is also the general value in the ancient slag. However only slag is excavated in the residential area at Beopcheonsaji site and there is no iron making relic. In addition, the result of principal component analysis contains that the total Fe-content of Beopcheonsaji site is 52 to 57%, and modified rate is 8 to 14%. It shows that the total Fe-content of Beopcheonsaji site is higher than relic from Gyesil-ri and Yeonje-ri and the modified rate is lower than other sites. This results mean that recollecting rate of Fe in Beopcheonsaji site is lower than other sites. Also, as a result of minor elements analysis, the slag from Gyesil-ri has the higher level of Ti, V and Zr than other sites and the microstructure are observed as magnetite and ulvospinel, so that the raw material of slag is iron sand. But the slag from Yeonje-ri and Beopcheonsaji site are identified to use iron ore. As a result of microstructure observation, fayalite, gray-columnar crystal, is found in the slag from Yeonje-ri and big wustite as main phase is observed in the slag from Beopcheonsaji site. This study show that the slag from Yeonje-ri is made of smelt ash produced during smelting works and the slag from Beopcheonsaji site is made of forging ash produced during forging work concerning the excavated location and the microstructure.

• The Journal of Engineering Geology
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• v.15 no.4 s.42
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• pp.447-462
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• 2005

The purposes of this study are to evaluate and discuss the importance of geochemical properties of soil materials that play an important role in the occurrence of the landslide, using analyses of microtexture, particle size distribution, XRC, and FE-SEM equipped with energy dispersive spectrum on soils collected from landslide slopes of gneiss, granite and sedimentary rock areas. Soils from gneiss and granite areas where landslides took place have much clay content relative to those from non landslide areas, particularly pronounced in the granite area. Therefore the clay content is considered a sensitive factor on landslide. Clay minerals contained in soils are illite, chlorite, kaolinite and montmorillonite. Especially the content of clay minerals in soils from the Tertiary sedimentary rocks is highest, with abundant montmorillonite as expandable species. It is believed that this area was much vulnerable to landslide comparable to other areas because of its high content of monoorillonite, even though there might be weak precipitation. Since no conspicuous differentiation in mineralogy between the landslide area and non landslide area can be made, the occurrence of landslide may be influenced not by mineralogy, but by local geography and mechanical properties of soils. Geochemical information on weathering properties, mineralogy, and microtexture of soils is helpful to better understand the causes and patterns of landslide, together with engineering geological analyses.

• Economic and Environmental Geology
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• v.35 no.3
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• pp.241-255
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• 2002

The purpose of this study is to investigate environmental geochemical characteristics for the acid mine drainage and stream sediments in the abandoned Honam coal mine area. For the chemical analysis, stream winter samples were collected at 54 sites and for the mineralogical and chemical analysis, stream sediments samples were collected at 34 sites. Physical and chemical characteristics of stream water were measured at the site and chemical compositions were analyzed by ICP-AES, ICP-MS and IC. Mineralogical characteristics of stream sediments samples were determined using XRD, SEM and EDS. In physical and chemical properties, stream water shows thats pH 2.85~8.12, Eh -62~215 mV, EC 0.205~146 ms/m, ER 0.234~255 {$\Omega}{\cdot}$m, DO 0.03~1068 mg/L and TDS 10.96~1420mg/L. In chemical compositions, we obtain that K 0.118~3.184 mg/L, Mg 2.1~114.48 mg/L, Ca 2.59~l25.02 mg/L, Al 0.01~44.72 mg/L, Fe 0.108~89.49 mg/L and Na 5.45~125.41 mg/L. Stream sediments are commonly composed of quartz, illite and goethite in the result of x-ray diffraction. After heat treatment at 98$0^{\circ}C$, the hematite peaks are distinctly shown. In consideration of heavy metals (include Fe) for steam sediments, Fe ranges 22575~34713 ppm, Zn 41.66~970.3 ppm, Cd 0.52~52.07 ppm, Cu 1.25~198.5 ppm and Pb 0.43~77.35 ppm.

• Korean Journal of Heritage: History & Science
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• v.53 no.4
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• pp.100-117
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• 2020

National Treasure no. 101, the stupa of State Preceptor Jigwang from the Beopcheonsa Temple Site in Wonju has been transferred from place to place and reassembled several times since it was built. In particular, overall dismantling and repair was carried out in 1957 to restore parts damaged by bombing during the Korean War. Documented information on the repair process and materials used at that time does not exist. However, various types of metal materials used for this stupa have been identified during conservation work. Besides clamps anchor bolts, 9mm-thick circular rebars were mainly used for joining the parts of this stupa, while circular rebars and wires of various thicknesses were used for joining the parts with mortar restoration materials. Although deformed bars are typically used for stone pagodas classified as architectural structures, smooth circular rebars were used in this case. In terms of restoration using mortar, material shapes were transformed, bound alternately, and twisted irregularly to improve bonding strength and coherence in order to insert restoration materials and to bolster structural weaknesses. In addition, metallographic analysis showed the material to be hypo-eutectoid steel with low carbon content. Many non-metallic inclusions in the shape of drops of different sizes were included, which do not affect the whole elemental composition due to the very small quantities involved. Qualitative and EPMA analysis of Mn and S, which were not identified by SEM-EDS area analysis, established an even distribution of MnS in crystal grains of the microstructure, regardless of the shape of the samples. It is presumed that secondary homogenization and softening might have been conducted after manufacturing to facilitate the working process. Furthermore, in consideration of properties indicating that the thinner the steel is, the less carbon content contained and the greater the elasticity and elongation, it is judged that restoration work was ordered.

• Journal of the Korean Society of Groundwater Environment
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• v.7 no.3
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• pp.103-115
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• 2000

The formation of brown-colored precipitates is one of the serious problems frequently encountered in the development and supply of groundwater in Korea, because by it the water exceeds the drinking water standard in terms of color. taste. turbidity and dissolved iron concentration and of often results in scaling problem within the water supplying system. In groundwaters from the Pajoo area, brown precipitates are typically formed in a few hours after pumping-out. In this paper we examine the process of the brown precipitates' formation using the equilibrium thermodynamic and kinetic approaches, in order to understand the origin and geochemical pathway of the generation of turbidity in groundwater. The results of this study are used to suggest not only the proper pumping technique to minimize the formation of precipitates but also the optimal design of water treatment methods to improve the water quality. The bed-rock groundwater in the Pajoo area belongs to the Ca-$HCO_3$type that was evolved through water/rock (gneiss) interaction. Based on SEM-EDS and XRD analyses, the precipitates are identified as an amorphous, Fe-bearing oxides or hydroxides. By the use of multi-step filtration with pore sizes of 6, 4, 1, 0.45 and 0.2 $\mu\textrm{m}$, the precipitates mostly fall in the colloidal size (1 to 0.45 $\mu\textrm{m}$) but are concentrated (about 81%) in the range of 1 to 6 $\mu\textrm{m}$in teams of mass (weight) distribution. Large amounts of dissolved iron were possibly originated from dissolution of clinochlore in cataclasite which contains high amounts of Fe (up to 3 wt.%). The calculation of saturation index (using a computer code PHREEQC), as well as the examination of pH-Eh stability relations, also indicate that the final precipitates are Fe-oxy-hydroxide that is formed by the change of water chemistry (mainly, oxidation) due to the exposure to oxygen during the pumping-out of Fe(II)-bearing, reduced groundwater. After pumping-out, the groundwater shows the progressive decreases of pH, DO and alkalinity with elapsed time. However, turbidity increases and then decreases with time. The decrease of dissolved Fe concentration as a function of elapsed time after pumping-out is expressed as a regression equation Fe(II)=10.l exp(-0.0009t). The oxidation reaction due to the influx of free oxygen during the pumping and storage of groundwater results in the formation of brown precipitates, which is dependent on time, $Po_2$and pH. In order to obtain drinkable water quality, therefore, the precipitates should be removed by filtering after the stepwise storage and aeration in tanks with sufficient volume for sufficient time. Particle size distribution data also suggest that step-wise filtration would be cost-effective. To minimize the scaling within wells, the continued (if possible) pumping within the optimum pumping rate is recommended because this technique will be most effective for minimizing the mixing between deep Fe(II)-rich water and shallow $O_2$-rich water. The simultaneous pumping of shallow $O_2$-rich water in different wells is also recommended.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.6 no.3
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• pp.171-178
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• 2008

Metal filter elements were newly introduced to the high temperature filter(HTF) system in the low- and intermediate-level radioactive waste vitrification plant. In order to evaluate the performance of various metal materials as filter media, elements made of AISI 316L, AISI 904L, and Inconel 600 were included to the test set of filter elements. At the visual inspection to the elements performed after completion of each test, a few dark spots were observed on the surface of some elements. Especially they were found much more at the AISI 316L elements than others. To check the dark spots are the corrosion phenomena or not, two kinds of analyses were performed to the tested filter elements. Firstly, the surfaces or the cross sections of filter specimens cut out from both normal area and dark spot area of elements were analyzed by SEM/EDS. The results showed that the dark spots were not evidences of corrosion but the deposition of sodium, sulfur and silica compounds volatilized from waste or molten glass. Secondly, the ring tensile strength were analyzed for the ring-shape filter specimens cut out from each kind of element. The result obtained from the strength tested showed no evidence of corrosion as well. Conclusionally, depending on the two kinds of analysis, no evidences of corrosion were found at the tested metal filter elements. But the dark spots formed on the surface could reduce the effective filtering area and increase the overall pressure drop of HTF system. Thus, continuous heating inside filter housing up to dew point will be required normally. And a few long-period test should be followed for the exact evaluation of corrosion of the metal filter elements.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.135-135
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• 2018

천이금속 질화물 코팅은 우수한 기계적 특성들로 인해 공구 코팅으로 많이 사용 되어왔다. 그 중에서도 특히 Cr계 경질 코팅은 높은 경도와 낮은 표면조도, 우수한 마찰특성 등 뛰어난 기계적 특성을 나타내므로 공구 코팅으로의 적용 가능성이 크다. 그러나 최근 공구산업의 발전으로 인해 공구가 더욱 가혹한 환경에서 사용됨에 따라, 공구의 수명을 향상시키고 보호하기 위해 코팅의 높은 밀착력이 요구되고 있으며, 모재와 코팅 사이에 중간층을 합성함으로써 공구의 밀착력을 향상시키는 연구가 활발히 진행되고 있다. 이전 연구에서 모재/중간층/코팅간의 경도와 탄성계수 비율(H/E ratio)의 구배가 코팅의 밀착력에 큰 영향을 미치는 것으로 확인되었다. 그러므로, WC 모재와 Cr계 코팅의 중간값의 H/E ratio를 갖는 중간층의 합성을 통해 코팅의 밀착력을 향상시킬 수 있을 것으로 판단된다. 본 연구에서는, 코팅의 밀착력을 향상시키기 위해 다양한 중간층을 증착한 CrZrN, CrAlN 코팅을 비대칭 마그네트론 스퍼터링 장비를 이용하여 합성하였다. 모재로는 디스크 형상의 WC-6wt.%Co 시편을 사용하였고 Cr, Zr, Si, Al single 타겟을 이용하여 Cr, CrN, CrZrN, CrZrSiN 등의 중간층이 증착된 코팅을 합성했다. 코팅의 합금상, 경도 및 탄성계수, 미세조직 및 조성, 표면 조도을 확인하기 위해 X-ray diffractometer (XRD), Fischer scope, field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), atomic force microscopy를 사용하였고, 코팅의 밀착 특성을 분석하기 위해 scratch tester와 optical microscopy (OM)를 이용하였다. 코팅의 내열성을 확인하기 위해 코팅을 furnace에 넣어 공기중에서 500, 600, 700, 800, 900, $1,000^{\circ}C$로 30분 동안 annealing 한 후에 nano-indentation을 사용하여 경도를 측정하였다. CrZrN 및 CrAlN 코팅을 나노 인덴테이션으로 분석한 결과, 모든 코팅의 경도(33.4-35.8 GPa)와 탄성계수(384.1-391.4 GPa)는 중간층의 종류에 상관없이 비슷한 값을 보인 것으로 확인됐다. 그러나, 코팅의 마찰계수는 중간층의 종류에 따라 다른 값을 보였다. CrZrN 코팅의 경우 CrN 합금상 중간층을 갖을 때 가장 낮은 값을 보였으며, CrAlN 코팅의 경우 CrN/CrZrSiN 중간층을 증착하였을때 마찰계수는 0.34로 CrZrN 중간층을 증착하였을 때(0.41)에 비해 낮은 값을 보였다. 또한, 코팅의 마모율 및 마모폭도 비슷한 경향을 보인 것으로 보아, CrN/CrZrSiN 중간층을 합성한 CrAlN 코팅의 내마모성이 상대적으로 우수한 것으로 판단된다. 코팅의 밀착력의 경우도 마찰계수와 비슷한 경향을 보였다. 이것은 중간층의 H/E ratio가 코팅의 내마모성에 미치는 영향에 의한 결과로 사료된다. H/E ratio는 파단시의 최대 탄성 변형율로써, 모재/중간층/코팅의 H/E ratio 구배에 따라 코팅 내의 응력의 완화 정도가 변하게 된다. WC 모재 (H/E=0.040)와 CrAlN 코팅(H/E=0.089) 사이에서 CrN, CrZrSiN 중간층의 H/E ratio는 각각 0.076, 0.083으로 모재/중간층/코팅의 H/E ratio 구배가 점차 증가함을 확인 할 수 있었고, 일정 응력이 지속적으로 가해지면서 진행되는 마모시험중에 CrN과 CrZrSiN 중간층이 WC와 CrAlN 코팅 사이에서 코팅 내부의 응력구배를 완화시키는 역할을 함으로써 CrAlN 코팅의 내마모성이 향상된 것으로 판단된다. 모든 코팅을 열처리 후 경도 분석 결과, CrN/CrZrSiN 중간층을 증착한 CrAlN 코팅은 $1,000^{\circ}C$까지 약 28GPa의 높은 경도를 유지한 것으로 확인 되었고, 이는 CrZrSiN 중간층 내에 존재하는 SiNx 비정질상의 우수한 내산화성에 의한 결과로 판단된다.

• Journal of Conservation Science
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• v.32 no.4
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• pp.579-588
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• 2016

This study analyzed nonmetallic inclusions in iron swords with a ring pommel excavated in the Ipbuk-dong, Suwon. Scanning electron microscopy with energy dispersive spectroscopy(SEM-EDS) was used to estimate the iron-making temperature, and we compared the oxide with $SiO_2$ to investigate the heat-treatment technology in the production of iron swords with a ring pommel by investigating the artificial insertion of a slag former and the metallurgical structure. From the wustite observed in most of the specimens, it is judged that these swords were produced by heating and forging iron smelted at a low temperature using the solid reduction method. In addition, judging from the partial presence of $P_2O_5$, it is assumed that they were smelted directly with natural ore, not calcined. From the ratios of $CaO/SiO_2$ and $TiO_2/SiO_2$, it is judged that the raw material for iron-making was iron ore and that a calcareous slag former was not artificially inserted. The structure of the blade part on the front end was pure iron. From the high carbon content of the blade part on the ring pommel and the formation of a martensitic structure and pearlite colony, it is judged that they were tempered after carburizing and that the back, handle part, and ring pommel were unintentionally carburized. Judging from the structure of these specimens, it was noted that they were produced by applying artificial partial heat-treatment technology. This study attempted to present a more scientific analysis by using the method of interpretation through component analysis of nonmetallic inclusions appearing in one relic by the ratio of the oxide divided by $SiO_2$. It is judged that reinterpreting the arguments by the results of the existing analysis and research in this way can obtain different interpretations.

• Economic and Environmental Geology
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• v.38 no.2 s.171
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• pp.187-196
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• 2005

Structural sites which cations can occupy in garnet structure are centers of the tetrahedron, octahedron, and distorted cube sharing edges with the tetrahedron and octahedron. Among them, the size of cation occuping at tetrahedral site (the center of tetrahedron) is closely related with the size of a unit cell of garnet. Accordingly, garnet containing iron with relative large ionic radii in tetrahedral site can be considered as a promising matrix for the immobilization of the elements with large ionic radii, such as actinides in radioactive wastes. We synthesized several garnets with the batch composition of $Ca_{1.5}GdCe_{0.5}ZrFeFe_3O_{12}$, and studied their properties and phase relations under various conditions. Mixed samples were fabricated in a pellet form under a pressure of $200{\~}400{\cal}kg/{\cal}cm^2$ and were sintered in the temperature range of $1100\~1400^{\circ}C$ in air and under oxygen atmospheres. Phase identification and chemical analysis of synthesized samples were conducted by XRD and SEM/EDS. In results, garnet was obtained as the main phase at $1300^{\circ}C$, an optimum condition in this system, even though some minor phases like perovskite and unknown phase were included. The compositions of garnet and perovskite synthesized from the batch composition of $Ca_{1.5}GdCe_{0.5}ZrFeFe_3O_{12}$ were ranged $[Ca_{l.2-1.8}Gd_{0.9-1.4}Ce_{0.3-0.5}]^{VIII}[Zr_{0.8-1.3}Fe_{0.7-1.2}]^{VI}[Fe_{2.9-3.1}]^{IV}O_{12}$ and $Ca_{0.1-0.5}Gd_{0.0-0.8}Ce_{0.1-0.5}\;Zr_{0.0-0.2}Fe_{0.9-1.1}O_3$, respectively. Ca content was exceeded and Ce content was depleted in the 8-coordinated site, comparing to the initial batch composition. This phenomena was closely related to the content of Zr and Fe in the 6-coordinated site.