• 제목/요약/키워드: Phase stability

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Non-astronomical Tides and Monthly Mean Sea Level Variations due to Differing Hydrographic Conditions and Atmospheric Pressure along the Korean Coast from 1999 to 2017 (한국 연안에서 1999년부터 2017년까지 해수물성과 대기압 변화에 따른 계절 비천문조와 월평균 해수면 변화)

  • BYUN, DO-SEONG;CHOI, BYOUNG-JU;KIM, HYOWON
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.26 no.1
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    • pp.11-36
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    • 2021
  • The solar annual (Sa) and semiannual (Ssa) tides account for much of the non-uniform annual and seasonal variability observed in sea levels. These non-equilibrium tides depend on atmospheric variations, forced by changes in the Sun's distance and declination, as well as on hydrographic conditions. Here we employ tidal harmonic analyses to calculate Sa and Ssa harmonic constants for 21 Korean coastal tidal stations (TS), operated by the Korea Hydrographic and Oceanographic Agency. We used 19 year-long (1999 to 2017) 1 hr-interval sea level records from each site, and used two conventional harmonic analysis (HA) programs (Task2K and UTide). The stability of Sa harmonic constants was estimated with respect to starting date and record length of the data, and we examined the spatial distribution of the calculated Sa and Ssa harmonic constants. HA was performed on Incheon TS (ITS) records using 369-day subsets; the first start date was January 1, 1999, the subsequent data subset starting 24 hours later, and so on up until the final start date was December 27, 2017. Variations in the Sa constants produced by the two HA packages had similar magnitudes and start date sensitivity. Results from the two HA packages had a large difference in phase lag (about 78°) but relatively small amplitude (<1 cm) difference. The phase lag difference occurred in large part since Task2K excludes the perihelion astronomical variable. Sensitivity of the ITS Sa constants to data record length (i.e., 1, 2, 3, 5, 9, and 19 years) was also tested to determine the data length needed to yield stable Sa results. HA results revealed that 5 to 9 year sea level records could estimate Sa harmonic constants with relatively small error, while the best results are produced using 19 year-long records. As noted earlier, Sa amplitudes vary with regional hydrographic and atmospheric conditions. Sa amplitudes at the twenty one TS ranged from 15.0 to 18.6 cm, 10.7 to 17.5 cm, and 10.5 to 13.0 cm, along the west coast, south coast including Jejudo, and east coast including Ulleungdo, respectively. Except at Ulleungdo, it was found that the Ssa constituent contributes to produce asymmetric seasonal sea level variation and it delays (hastens) the highest (lowest) sea levels. Comparisons between monthly mean, air-pressure adjusted, and steric sea level variations revealed that year-to-year and asymmetric seasonal variations in sea levels were largely produced by steric sea level variation and inverted barometer effect.

Changes of Mineralogical Characteristics of Precipitates in Acid Mine Drainage of the Dalsung Mine and Related Changes of Trace Elements (달성광산 산성광산배수 침전물의 시간에 따른 광물상 특성 변화 및 이에 따른 미량원소의 거동 변화)

  • Yoon, Young Jin;Kim, Yeongkyoo;Lee, Seong-joo
    • Economic and Environmental Geology
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    • v.55 no.5
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    • pp.531-540
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    • 2022
  • Various iron minerals that precipitate in acid mine drainage have a great influence on the concentration change and mobility of trace elements in the drainage during phase transition to other minerals as well as the precipitation process. This study investigated the change of mineral properties and the behaviors of trace elements influenced by pH and time for the precipitates collected from the acid mine drainage treatment system of the Dalsung mine, where schwertmannite is mainly precipitated. However, the main mineral precipitated in the drainage was goethite, suggesting schwetmannite has already undergone a phase transition to goethite to some extent, and it was observed that at higher pH, the peak width at half maximum of XRD peak was narrower. This can be interpreted as the transformation of small amount of amorphous schwetmannite to goethite or an increase in the crystallinity of goethite, and it showed that the higher the pH, the greater this change was. The concentration of Fe was also greatly affected by the pH values, and as the pH increased, the concentration of Fe in the drainage decreased. With increasing time, the Fe concentration increased and then decreased, which can be interpreted to indicate the dissolution of schwertmannite and precipitation of goethite. This mineral change probably resulted in the rapid increase of the concentration of S at initial stage, but its concentration was stabilized later. The concentration of S is also related to the stability of schwetmannite, showing a high concentration at a low pH at which schwertmannite is stable and a low concentration at a high pH at which goethite is stable. The trace elements present as cations in the drainage also showed a close relationship with the pH, generally the lower the pH, the higher the concentration, due to the solubility changes by the pH, and the precipitation and the changes in mineral surface charge at high pH. On the other hand, in the case of As, existing as an anion, although it showed a high concentration at low pH, its concentration increased with time at all pH values, which is probably related to the concentration of Fe which can be coprecipitated in the drainage, and the increase of As concentration with time is also considered to be related to the decrease in schwertmannite rather than the mineral surface charge.

Partial Oxidation of Methane to $H_2$ Over Pd/Ti-SPK and Pd/Zr-SPK Catalysts and Characterization (Pd/Ti-SPK과 Pd/Zr-SPK 촉매상에서 수소 생산을 위한 메탄의 부분산화반응과 촉매의 특성화)

  • Seo, Ho-Joon;Kang, Ung-Il
    • Applied Chemistry for Engineering
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    • v.21 no.6
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    • pp.648-652
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    • 2010
  • Catalytic activities of the partial oxidation of methane (POM) to hydrogen were investigated over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK in a fixed bed flow reactor (FBFR) under atmosphere, and the catalysts were characterized by BET, XPS, XRD. The BET surface areas, pore volume and pore width of Horvath-Kawaze, micro pore area and volume of t-plot of Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were $284m^2/g$, $0.233cm^3/g$, 3.9 nm, $30m^2/g$, $0.015cm^3/g$ and $396m^2/g$, $0.324cm^3/g$, 3.7nm, $119m^2/g$, $0.055cm^3/g$, repectively. The nitrogen adsorption isotherms were type IV with hysteresis. XPS showed that Si 2p and O 1s core electronlevels of Ti-SPK and Zr-SPK substituted Ti and Zr shifted to slightly lower binding energies than SPK. The oxidation states of Pd on the surface of catalysts were $Pd^0$ and $Pd^{+2}$. XRD patterns showed that crystal structures of fresh catalyst changed amorphous into crystal phase after reaction. The conversion and selectivity of POM to hydrogen over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were 77, 84% and 78, 72%, respectively, at 973 K, $CH_4/O_2$ = 2, GHSV = $8.4{\times}10^4mL/g_{cat}{\cdot}h$ and were kept constant even after 3 days in stream. These results confirm superior activity, thermal stability, and physicochemical properties of catalyst in POM to hydrogen.

Analysis of Physicochemical Characterization and Volatiles in Pure or Refined Olive Oils (국내 유통되는 퓨어 및 정제 올리브유의 이화학적 특성 및 향기 분석)

  • Nam, Ha-Young;Lee, Ju-Woon;Hong, Jang-Hwan;Lee, Ki-Teak
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.36 no.11
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    • pp.1409-1416
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    • 2007
  • Seven selected commercial pure or refined olive oils were obtained from the market, and their physicochemical properties and volatile characterizations were investigated. Fatty acid profiles of the analyzed olive oils showed oleic $(61.2{\sim}74.7mole%)$, palmitic $(10.2{\sim}16.8mole%)$, linoleic $(9.4{\sim}18.0mole%)$, stearic $(1.9{\sim}3.0mole%)$, palmitoleic $(0.7{\sim}2.4mole%)$ and linolenic acid $(0.5{\sim}0.9mole%)$. According to Hunter#s color measurement, pure or refined olive oils showed $L^*$ value of $92.2{\sim}99.0$, $a^*$ value of $-22.2{\sim}-3.2$, and $b^*$ value of $18.5{\sim}55.0$. Their total phenol contents ranged from 1.9 to $13.3mg/100g$ while ${\alpha}-tocopherol$ content showed $7.91{\sim}13.88mg/100g$. Oxidation stability of the pure or refined olive oils were observed by Rancimat. The induction period ranged from 17.37 to 34.72 hr while their POV were $6.83{\sim}20.31meq/kg$ oil. Electronic nose and gas chromatograph-mass spectrometry with head-space solid phase microextraction were applied to identify and discriminate the volatile compounds and flavors in pure or refined olive oils, respectively.

Mineralogy and Genesis of Hydrothermal Deposits in the Southeastern Part of Korean Peninsula : (5) Deogbong Napseok Deposit (우리나라 동남부 지역의 열수광상에 대한 광물학적 및 광상학적 연구:(5) 덕봉납석광상)

  • Kim, Soo-Jin;Choo, Chang-Oh;Kim, Won-Sa
    • Journal of the Mineralogical Society of Korea
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    • v.7 no.1
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    • pp.25-39
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    • 1994
  • The Deogbong napseok clay deposit which is composed mainly of dickite and pyrophyllite has been formed by hydrothermal alteration of the Late Cretaceous volcanic rocks consisting of andesitic tuff and andesite. The mineralogy of the napseok ores and the hydrothermal alteration processes have been studied in order to know the nature of the interaction between minerals and fluids for the formation of the deposit. Chemical distribution shows that alkali elements and silica were mobile but alumina was relatively immobile during the hydrothermal processes. It is evident that enrichment of alumina and leaching of silica from the host rock led to the formation of the napseok ore, whereas the enrichment of silica in the outer zone of the deposit gave rise to the silica zone. A large amount of microcrystalline quartz closely associated with dickite and pyrophyllite suggests the increasing activity of silica. Thus Si which was released away from the argillic zone by the increasing activity of silica. Thus Si which was released away from the argillic zone by the increasing activity of silica solubility moved out precipitating in the margin of the deposit to form the silica zone. Variation in dickite crystallinity implies the local change in the stability of the system. Thermodynamic calculation shows that the invariant point of pyrophyllite-dickite (kaolinite)-diaspore-quartz assemblages at 500 bars in the system $Al_{2}O_{3}-SiO_{2}-H_{2}O$ is about 300 $^{\circ}C$. Based on the mineral assemblages and the experimental data reported, it is estimated that the main episode of hydrothermal alteration occurred at least above 270 to 300 $^{\circ}C$ and $X_{CO_2}$ <0.025. Mineral occurrence and chemical variation indicate that the activity of Al is high in the upper part of the deposit, whereas the activity of Si is high in the lower part and the margin of the deposit. The nonequilibrium phase relations observed in the Deogbong deposit might be due to local change in intensive thermodynamic variables and fluid transport properties that resulted in the formation of nonequilibrium phases b of several stages.

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Hydrochemistry of Groundwater at Natural Mineral Water Plants in the Okcheon Metamorphic Belt (옥천계변성암 지역의 먹는샘물 지하수의 수리지구화학적 특성)

  • 추창오;성익환;조병욱;이병대;김통권
    • Journal of Korea Soil Environment Society
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    • v.3 no.3
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    • pp.93-107
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    • 1998
  • Because of its stable quantity and quality, groundwater has long been a reliable source of drinking water for domestic users. Rapid economic growth and rising standards of living have in recent years put severe demands on drinking water supplies in Korea. Groundwaters that are currently being used for natural mineral water were hydrochemically evaluated and investigated in order to maintain their quality to satisfy strict health standards. There exist 15 natural mineral water plants in the Okcheon metamorphic belt. Characteristics of groundwaters are different from those of other areas in that electrical conductivity, hardness, contents of Ca, Mg and $HCO_3$are relatively high. The content of major cations is in the order of Ca>Mg, Na>K, whereas that of major anions shows the order of $HCO_3$>$SO_4$>Cl>F. The fact that the Ca-Mg-HCO$_3$type is mostly predominant among water types reflects that dissolution of carbonates that are abundantly present in the metamorphic rocks plays an important part in groundwater chemistry. Representative correlation coefficients between chemical species show Mg-$HCO_3$(0.92), Ca-$HCO_3$(0.88), Ca-Mg(0.80), Ca-Cl(0.78), Mg-$SO_4$(0.78), Ca-$SO_4$(0.71), possibly due to the effect by dissolution of carbonates, gypsum or anhydrite. Determinative coefficients between some chemical species represent a good relationship, especially for EC-(K+Na+Ca), Ca-$HCO_3$, Ca-Mg, indiacting that they are similar in chemical behaviors. According to saturation index, most chemical species are undersaturated with respect to major minerals, except for some silica phases. Groundwater is slightly undersaturated with respect to calcite and dolomite, whereas it is still greatly undersaturated with respect to gypsum, anhydrite and fluorite, Based on the Phase equilibrium in the systems $NA_2$O-$Al_2$$O_3$-$SiO_2$-$H_2$O and $K_2$O-$Al_2$$O_3$-$SiO_2$-$H_2$O, it is clear that groundwater is in equilibrium with kaolinite, evolved from the stability area of gibbsite during water-rock interaction. It is expected that chemical evolution of groundwater continue to proceed with increasing pH by reaction of feldspars, with calcite much less reactive.

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Mineralogical and chemical characterization of arsenic solid phases in weath-ered mine tailings and their leaching potential (풍화광미내 고상 비소의 광물학적${\cdot}$화학적 특성 및 용출 가능성 평가)

  • 안주성;김주용;전철민;문희수
    • Economic and Environmental Geology
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    • v.36 no.1
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    • pp.27-38
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    • 2003
  • Arsenic contamination around Au-Ag mining areas occurs mainly from the oxidation of arsenopyrite which is frequently contained in mine tailings. In weathered tailings, oxidation of sulfide minerals typically results in the formation of abundant ferric (oxy)hydroxides or (oxy)hydroxysulfates near the tailings surface, and arsenic may be associated with these secondary precipitates. In this study, solid phases of arsenic in weathered tailings of some Au-Ag mines were investigated through the SEM/EDS and sequential extraction analyses. The stability of As solid phases and the leaching potential were assessed with the variation of pH and Eh conditions. Oxidation of sulfides in the tailings samples was indicated by depletion of S molar concentrations compared to As and heavy metals. Under XRD examinations, jarosite as an Fe-oxyhydroxysulfate was found in the tailings of Deokeum, Dongil and Dadeok, and scorodite as an As-bearing crystalline mineral was identified from Dadeok which has the highest concentration of As (4.36 wt.%). Beudantite-like phases and some Pb-arsenates were also found under SEM/EDS analysis, and most of As phases were associated with Fe-(oxy)hydroxides and (oxy)hydroxysulfates despite a few arsenopyrite from Samgwang and Gubong. Sequential extraction analysis also showed that As was present predominantly as coprecipitated with Fe hydroxides from Dongil, Dadeok and Myungbong (72∼99%), and as sulfides (58%) and Fe hydroxide-associated forms (40%) from Samgwang and Gubong. In the tailings leaching experiment, As was released with high amounts by the dissolution of As-bearing Fe(oxy)hydroxysulfates in the lowest pH (2.7) conditions of Deokeum, and by desorption under alkaline conditions of Samgwang and Gubong. Higher leaching rates of arsenite(+3) were found under acidic conditions, which pose a higher risk to water quality. Changes in pH and Eh conditions coupled with microbial processes could influence the stabilities of the As solid phases, and thus, time amendments or landfilling of weathered tailings may result in enhanced As mobilization.

Hydrochemical Characteristics of Natural Mineral Water in the Daebo and Bulguksa Granites (대보화강암과 불국사화강암지역 먹는샘물의 수리화학적 특성)

  • 조병욱;성익환;추창오;이병대;김통권
    • The Journal of Engineering Geology
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    • v.8 no.3
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    • pp.247-259
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    • 1998
  • Groundwater quality of the natural mineral water was investigated in hydrochemical aspects in order to ensure that mineral water meets stringent health standards. There exist 20 mineral water plants in the Daebo granite and 4 mineral water plants in the Bulguksa granite, respectively. Both granite areas show some differences in water chemistry. The pH, EC, hardness, total ionic contents in groundwater of the Daebo granite area are higher relative to those of the Bulguksa granite area. The content of major cations is in the order of Ca>Na>Mg>K, while that of major anions shows the order of $HCO_3>SO_4$>Cl>F. The fact that the $Ca-Na-HCO_3$ type is most predominant among water types may reflect that the dissolution of plagioclase that is most abundant in granitic rocks plays a most important role in groundwater chemistry. Representative correlation coefficients between chemical species are variable depending on geology. In the Daebo granite area, $Ca-HCO_3(0.84),{\;}Mg-HCO_3(0.81),{\;}SiO_2-Cl(0.74),{\;}Na-HCO_3(0.70)$ show relatively good correlationships. In the Bulguksa granite area, fairly good correlationships are found among some components such as K-Mg(0.93), $K-HCO_3(0.92)$, Mg-Cl(0.92), $Cl-HCO_3(0.91)$, and K-F(0.90). According to saturation index, most chemical species are undersaturated with respect to major minerals, except for some silica phases. Groundwater is slightly undersaturated with respect to calcite, whereas it is still greatly undersaturated with respect to dolomite, gypsum and fluorite. Based on the phase equilibrium it is clear that groundwater is mostly in equilibrium with kaolinite and becomes undersaturated with respect to feldspars, evolved from the stability area of gibbsite during water-rock interaction. While the activity of silica increases, there is no remarkable increase in the acivities of alkali ions and pH, which indicates that some amounts of silicic acid dissolved from silica phases as well as feldspars were provided to groundwater. It is concluded that chemical evolution of groundwater in granite aquifers may continue to proceed with increasing pH.

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Preparation and Oxygen Permeation Properties of La0.07Sr0.3Co0.2Fe0.8O3-δ Membrane (La0.07Sr0.3Co0.2Fe0.8O3-δ 분리막의 제조 및 산소투과 특성)

  • Park, Jung Hoon;Kim, Jong Pyo;Baek, Il Hyun
    • Applied Chemistry for Engineering
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    • v.19 no.5
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    • pp.477-483
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    • 2008
  • $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ oxide was synthesized by a citrate method and a typical dense membrane of perovskite oxide has been prepared using as-prepared powder by pressing and sintering at $1300^{\circ}C$. Precursor of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ prepared by citrate method was investigated by TGA and XRD. Metal-citrate complex in precursor was decomposed into perovskite oxide in the temperature range of $260{\sim}410^{\circ}C$ but XRD results showed $SrCO_3$ existed as impurity at less than $900^{\circ}C$. Electrical conductivity of membrane increased with increasing temperature but then decreased over $700^{\circ}C$ in air atmosphere ($Po_2=0.2atm$) and $600^{\circ}C$ in He atmosphere ($Po_2=0.01atm$) respectively due to oxygen loss from the crystal lattice. The oxygen permeation flux increased with increasing temperature and maximum oxygen permeation flux of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ membrane with 1.6 mm thickness was about $0.31cm^3/cm^2{\cdot}min$ at $950^{\circ}C$. The activation energy for oxygen permeation was 88.4 kJ/mol in the temperature range of $750{\sim}950^{\circ}C$. Perovskite structure of membrane was not changed after permeation test of 40 h and the membrane was stable without secondary phase change with 0.3 mol Sr addition.

Preparation of Ni-doped Gamma Alumina from Gibbsite and Its Characteristics (깁사이트로부터 니켈피착 감마알루미나의 제조 및 특성)

  • Lee, Hyun;Chung, In-Sung;Park, Hee-Chan
    • Korean Journal of Materials Research
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    • v.8 no.12
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    • pp.1158-1164
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    • 1998
  • Aluminium sulfate solution was prepared by sulfuric acid treatment from gibbsite. Aluminium sulfate hydrate [$Al_2(SO_4)_3$ · $nH_2O$] was precipitated from aluminium sulfate solution by adding it into ethylalcohol. From XRD analysis as-prepared $Al_2(SO_4)_3$ · $nH_2O$ was confirmed to have mixed-crystalization water(n=18, 16, 12, 6). The average water of crystalization calculated from thermogravimetry(TG) was 14.7. Aluminium sulfate hydrate [$Al_2(SO_4)_3$ · $nH_2O$] was thermally decomposed and converted to $Al_2(SO_4)_3$ at $800^{\circ}C$, $\gamma-Al_2O_3$ at $900-1000^{\circ}C$, and $\alpha-Al_2O_3$ at $1200^{\circ}C$. Ni-doped $\gamma-Al_2O_3$, was synthesized from the slurry of as-prepared $\gamma-Al_2O_3$, with the ratio of [Ni]/[Al]=0.5. The reaction conditions of synthesis were determined as initial pH 9.0 and temperature $80^{\circ}C$ The basicity(pH) of slurry was controlled by using urea and $NH_4OH$ solution. Urea was also used for deposition-precipitation. For determining termination of reaction, the data acquisition was performed by oxidation reduction potential(ORP), conductivity and pH value in the process of reaction. Termination of the reaction was decided by observing the reaction steps and rapid decrease in conductivity. On the other hand, BET(Brunauer, Emmett and Teller) and thermal diffusity of Ni- doped $\gamma-Al_2O_3$, with various content of Ni were measured and compared. Thermal stability of Ni- doped $\gamma-Al_2O_3$ at $1250^{\circ}C$ was confirmed from BET and XRD analysis. The surface state of Ni-doped $\gamma-Al_2O_3$ was investigated by X-ray photoelectron spectroscopy(XPS). The binding energy at $Ni2P_{3/2}$ increased with increasing the formation of $NiAl_2O_4$ phase.

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