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Synthesis of ceramic particles by hydrothermal method (수열법에 의한 세라믹분말 합성)

  • 김판채;최종건
    • Proceedings of the Korea Association of Crystal Growth Conference
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    • 1996.06b
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    • pp.219-222
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    • 1996
  • 수열법은 밀폐용기중에서 10$0^{\circ}C$이상의 가열, 가압된 수용액이 반응에 관여하는 것으로써, 수정, CaCO3, AlPO4, GaPO4 등과 같은 단결정의 육성 뿐만 아니라 균일분산계로부터 균일한 결정성의 미립자 합성에도 폭넓게 이용되고 있다. 세라믹분말의 합성에 있어서, 이 방법은 특히 형상, 입자크기의 제어가 용이할 뿐만 아니라 고상법, 졸-겔법, 공침법에서와 같은 열처리, 분쇄과정이 필요없기 때문에 고순도의 초미립자를 얻을 수 있는 장점이 있다. 근년 미국, 일본에서는 수열법을 이용한 유전, 압전체 등 세라믹분말의 일부가 공업적인 규모로 대량 생산되고 있다. 그러나 이에 대한 국내 기술은 아직 초기단계에 이르고 있는 실정이다. 따라서 본 연구실에서는 수열법에 의한 단결정 육성 (예; 자수정, CaCO3, AlPO4, GaPO4, KTP, Emerald 등), 박막제조 (예; GaP, PbTiO3, BaTiO3 등), 정제 (고령토, 장석, 도석 등), 원석처리 (진주, 인공 emerald, 비취 등) 그리고 각종 세라믹분말의 합성 등과 같은 다양한 기반기술의 축적과 동시에 공업화에 대응한 수열장치를 위하여 반응용기의 대형화, 엄밀한 밀폐방식, 실용적인 수열조건 등을 개발해 오고 있다. 본 발표에서는 현재까지의 연구개발 내용 중에서 결정성 미립자에 관련한 세라믹분말의 합성에 대한 일부의 결과들을 보고한다. 일반적으로 수열장치는 전기로, 반응용기, 온도 및 압력제어계 등을 기본으로 하고 있으며 시판용의 대부분이 교반기가 부착된 수직형 (vertical type)이다. 이와 같은 방식에 있어서는 엄밀한 밀폐가 곤란, 반응온도의 한계성 (25$0^{\circ}C$ 이하), 증진율의 한계성 (소량생산) 등과 같은 점이 있기 때문에 본 연구실에서는 개폐식 전기로내에 엄밀한 밀폐가 가능한 수평식(horizontal type)의 반응용기를 채택한 뒤 이를 회전 또는 시이소(seesaw)식으로 움직일 수 있도록 하여 연속공정화, 온도구배의 자율조절 그리고 보다 저온에서도 인위적인 이온의 확산을 효율적으로 유도할 수 있도록 하였다. 이와 같은 방식은 기존의 방식과 비교하여 반응용기 내에 응집현상과 미반응물이 존재하지 않으며 또한 단분산으로 결정성 미립자를 대량적으로 얻을 수 있는 장점이 있었다. 다음은 이상과 같이 본 연구실에서 자체 개발한 수열장치를 이용하여 PbTiO3, (Pb,La)TiO3Mn, BaTiO3, ZnSiO4:Mn, CaWO4 등과 같은 세라믹분말에 대한 합성 실험의 결과이다. 압전성, 초전성이 우수한 PbTiO3 및 (Pb,La)TiO3:Mn 분말의 수열합성은 PbO, TiO2, La2O3 등의 분말을 출발원료로 하여 합성도도 25$0^{\circ}C$부근의 알카리성 용액중에서 결정성 PbTiO3 및 (Pb,La)TiO3:Mn 미립자를 단상으로 얻었으며 입자의 형상 및 크기는 합성온도와 수열용매의 종류에 의존하였다. 유전체로서 폭넓게 응용되고 있는 BaTiO3 분말은 Ba(OH)2.8H2O, TiO2와 같은 최적의 출발원료를 선택함으로써 15$0^{\circ}C$ 부근의 저온영역에서도 용이하게 합성할 수 있었다. 특히 본 연구에서는 수용성인 Ba(OH)2.8H2O를 사용함으로써 host-guest적인 반응을 유도시키는데 있어 물의 가장 실용적이고 효과적인 수열용매임도 알았다. ZnSiO4:Mn, CaWO4, MgWO4와 같은 형광체 분말은 공업적으로 고상반응 또는 습식법에 의해 얻어지고 있으나 이들 방법에 있어서는 분쇄공정으로 인한 형광특성의 저하와 같은 문제점이 있다. 따라서 본 연구에서는 수열법을 이용하여 이들 화합물의 합성을 시도하였으며 그 결과 합성온도 30$0^{\circ}C$ 부근의 알칼리성 용액중에서 수열적으로 얻어짐을 알았다. 여기서의 합성분말을 이용하여 실제 조명램프로 제조한 결과 녹색, 청색 발광용 형광체로서 우수한 형광특성을 나타내었다. 천연에서 소량 산출되고 있는 고가의 (Li,Al)MnO2(OH)2:Co 분말은 도자기의 전사지용 청색안료로써 이용되고 있다. 본 연구실에서는 LiOH.H2O, Al(OH)3, MnO2 등의 분말을 출발원료로 하고 24$0^{\circ}C$ 온도 부근 그리고 물을 수열용매로 하여 천연산에 필적하는 (Li,Al)MnO2(OH)2:Co 분말을 인공적으로 합성하였다.

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Characterization of an Antarctic alkaline protease, a cold-active enzyme for laundry detergents (세탁세제 첨가용 효소 개발을 위한 남극 해양세균 유래 저온성 단백질분해효소의 특성 연구)

  • Park, Ha Ju;Han, Se Jong;Yim, Joung Han;Kim, Dockyu
    • Korean Journal of Microbiology
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    • v.54 no.1
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    • pp.60-68
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    • 2018
  • A cold-active and alkaline serine protease (Pro21717) was partially purified from the Antarctic marine bacterium Pseudoalteromonas arctica PAMC 21717. On a zymogram gel containing skim milk, Pro21717 produced two distinct clear-zones of approximately 37 kDa (low intensity) and 74 kDa (high intensity). These were found to have identical N-terminal sequences, suggesting they arose from an identical precursor and that the 37 kDa protease might homodimerize to the more active 74 kDa form of the protein. Pro21717 displayed proteolytic activity at $0-40^{\circ}C$ (optimal temperature of $40^{\circ}C$) and maintained this activity at pH 5.0-10.0 (optimal pH of 9.0). Notably, relative activities of 30% and 45% were observed at $0^{\circ}C$ and $10^{\circ}C$, respectively, in comparison to the 100% activity observed at $40^{\circ}C$, and this enzyme showed a broad substrate range against synthetic peptides with a preference for proline in the cleavage reaction. Pro21717 activity was enhanced by $Cu^{2+}$ and remained stable in the presence of detergent surfactants (linear alkylbenzene sulfonate and sodium dodecyl sulfate) and other chemical components ($Na_2SO_4$ and metal ions, such as $Ba^{2+}$, $Mg^{2+}$, $Ca^{2+}$, $Zn^{2+}$, $Fe^{2+}$, $K^+$, and $Na^{2+}$), which are often included in commercial detergent formulations. These data indicate that the psychrophilic Pro21717 has properties comparable to the well-characterized mesophilic subtilisin Carlsberg, which is commercially produced by Novozymes as the trademark Alcalase. Thus it has the potential to be used as a new additive enzyme in laundry detergents that must work well in cold tap water below $15^{\circ}C$.

Characterization and β-secretase Inhibitory Activity of Water-soluble Polysaccharides Isolated from Phellinus linteus Fruiting Body (상황버섯 자실체로부터 분리된 수용성 다당류의 특성 분석 및 이의 베타 시크리타아제 활성 저해효과)

  • Jo, Hang Soo;Choi, Doo Jin;Chung, Mi Ja;Park, Jae Kweon;Park, Yong Il
    • The Korean Journal of Mycology
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    • v.40 no.4
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    • pp.229-234
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    • 2012
  • A key molecule in the pathogenesis of Alzheimer's disease (AD) is the ${\beta}$-amyloid peptide ($A{\beta}$) generated by ${\beta}$-secretase activity, an aspartic protease. This study was designed to evaluate inhibitory effect of the high-molecular weight water-soluble polysaccharides (Et-P) isolated and purified from Phellinus linteus fruiting body on ${\beta}$-secretase activity. The Et-P was purified from the hot water extract of Phellinus linteus fruiting body mainly by 75% ethanol precipitation and DEAE-Cellulose column chromatography. From the DEAE-Cellulose chromato-gram and molecular weight analysis, the Et-P was shown to be a mixture of three polysaccharides with molecular mass of 1,629, 1,294, and 21 kDa, respectively. The monosaccharide composition of Et-P was determined to be glu-cose, galactose, and mannose as major sugars, glucose being the most prominent one (48% in mole percentage). The elemental analysis and FT-IR analysis suggested that Et-P is typical polysaccharides having at least partially ${\beta}$-linkages and possible existing as complex with phenolic compounds. The laminarinase digestion and HPAEC-PAD analysis suggested that Et-P is a variant of beta-(1,3)-glucans. The Et-P showed DPPH radical scavenging activity and, especially, a significant inhibitory activity on ${\beta}$-secreatase activity (48% inhibitin at 100 ${\mu}g/mL$), suggesting that they may inhibit the formation of $A{\beta}$ which is the major causative of Alzheimer's disease. The results of this study suggest that the water soluble polysaccharides of Phellinus linteus fruiting body can be a potent material for the development of preventive or therapeutic agents for AD.

Improvement of an Simultaneous Determination for Clenbuterol and Ractopamine in Livestock Products using LC-MS/MS (LC-MS/MS를 이용한 축산물 중 clenbuterol과 ractopamine의 동시 분석법 개선)

  • Cho, Yoon-Jae;Chae, Young-Sik;Kim, Jae-Young;Kim, Hyung-Soo;Kang, Ilhyun;Do, Jung-Ah;Oh, Jae-Ho;Kwon, Kisung;Chang, Moon-Ik
    • Korean Journal of Food Science and Technology
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    • v.45 no.1
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    • pp.25-33
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    • 2013
  • Clenbuterol and ractopamine, which are ${\beta}$-agonists, have been misused as a growth promoting agent in meat producing animals. Clenbuterol was banned for veterinary drug in Korea because of its problems regarding safety. Due to their adverse effects, such as cardiovascular and central nervous diseases on human health proper control and monitoring should be conducted. The existing analytical method of clenbuterol and ractopamine in the Food code was improved through our present study. The bovine muscle samples were subjected to enzymatic hydrolysis, extracted with ethyl acetate and defatted by hexane-methanol partitioning. A molecular imprinted polymer (MIP) solid phase extraction cartridge was used for clean-up and LC-MS/MS was operated in positive multiple reaction monitoring (MRM). Clenbuterol-$d_9$ and ractopamine-$d_3$ were used as an internal standard. The renewed method was validated according to the CODEX guideline. The limits of quantitation for clenbuterol and ractopamine were 0.2 and 0.5 ${\mu}g/kg$, respectively. The mean recoveries ranged in 104.2-113.5% for clenbuterol and in 107.6-118.1% for ractopamine. The improved method was able to save both time and expenses.

Analysis of Fungicide Prochloraz in Platycodi Radix by GC-ECD (GC-ECD를 이용한 한약재 길경(Platycodi Radix) 중 살균제 Prochloraz의 분석)

  • Oh, Gyeong-Seok;Yoon, Myung-sub;Yang, Seung-Hyun;Choi, Hoon
    • Korean Journal of Environmental Agriculture
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    • v.40 no.4
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    • pp.353-358
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    • 2021
  • BACKGROUND: Prochloraz has been widely used as an imidazole fungicide on fruits and vegetables in Korea. Analytical approaches to evaluate prochloraz residues in herbal medicine are required for their safety management. In this study, we developed a GC-ECD method for quantitative determination of prochloraz in Platycodi Radix. The metabolite 2,4,6-trichlorophenol (2,4,6-T) was used as a target compound to evaluate total prochloraz residues as it is categorized to a representative residue definition of prochloraz. All residues containing 2,4,6-T were converted to 2,4,6-T and subjected to GC-ECD. METHODS AND RESULTS: In order to verify the applicability, the method was optimized for determining prochloraz and it metabolite 2,4,6-T in Platycodi Radix. Prochloraz and its metabolite 2,4,6-T residuals were extracted using acetone. The extract was diluted with and partitioned directly into dichloromethane to remove polar co-extractives in the aqueous phase. The extract was decomposed to 2,4,6-T, and then the partitioned ion-associate was finally purified by optimized aminopropyl solid-phase extraction (SPE). The limits of quantitation of the method (MLOQs) were 0.04 mg/kg and 0.02 mg/kg, respectively for prochloraz and 2,4,6-T, considering the maximum residue level (MRL) of prochloraz as 0.05 mg/kg in Platycodi Radix. Recovery tests were carried out at two levels of concentration (MLOQ, 10 MLOQ) and resulted in good recoveries (82.1-89.7%). Good reproducibilities were obtained (coefficient of variation < 2.8%), and the linearities of calibration curves were reasonable (r2 > 0.9986) in the range of 0.005-0.5 ㎍/mL. CONCLUSION(S): The method developed in this study was successfully validated to meet the guidelines required for quantitative determination of pesticides in herbal medicine. Thus, the method could be useful to monitor prochloraz institutionally in herbal medicine.

Material Characteristics of Gold Artifacts of Sarira Reliquary inside Stone Pagoda of Mireuksa Temple Site (미륵사지 석탑 출토 사리장엄 금제유물의 재료학적 특성)

  • Kwon, Hyuk-nam;Yoo, Dong-wan;Lee, Jang-jon;Han, Min-su
    • Korean Journal of Heritage: History & Science
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    • v.47 no.4
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    • pp.210-223
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    • 2014
  • When sarira reliquary was found in stone pagoda of Mireuksa Temple, there were 494 gold artifacts, including inner gold pot, gold plate with inscription for Sarira enshrinement, etc. Most of gold artifacts were crafted, but there were 22 gold plates and 4 gold ingots, which did not have any specific shape. It was considered that they had not been crafted. Since gold exists as a metal rather than a metallic oxide in nature, in general, it can be crafted by melting and shaping. However, gold in nature has impurities so it has to be refined to have malleability. The characteristic features were identified through the analysis of gold artifacts from sarira reliquary found in stone pagoda of Mireuksa Temple. The analysis result showed that there were 3 types of gold; pure gold artifacts, artifacts produced with silver containing gold and natural gold ingots. Inner gold pot, gold earrings and gold small beads were produced with pure gold and they contained less than 1wt.% of copper. It seemed like they were produced as pure gold to be shaped by hammering. Gold plate with inscription, tweezers, gold earrings, ingots, etc. were produced with silver containing gold as they had to be more solid. Gold ingots seemed to be natural gold considering the distribution of silver and copper in them, but it cannot be concluded as there are not enough information on gold ingots in Korea. The comprehensive research on gold ingots from various regions in Korea has to be carried out to confirm the above. Sarira Reliquary showed the very sophisticated gold craftsmanship. Gold ingots with the inscriptions, which say 1 nyang, were approximately 14g. Considering the weight of these ingots as standard, weights of other ingots were half nyang(7g), 2 nyang(28g), etc.

Development of Analytical Method for Kasugamycin in Agricultural Products using LC-MS/MS (LC-MS/MS를 이용한 농산물 중 Kasugamycin 시험법 개발)

  • Lee, Han Sol;Do, Jung-Ah;Park, Ji-Su;Cho, Sung Min;Shin, Hye-Sun;Jang, Dong Eun;Jung, Yong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.3
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    • pp.235-241
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    • 2019
  • An analytical method was developed for the determination of an antibiotic fungicide, kasugamycin, in agricultural products (hulled rice, potato, soybean, mandarin and green pepper) using liquid chromatographytandem mass spectrometry (LC-MS/MS). Samples were extracted with methanol adjusted to pH 13 using 1 N sodium hydroxide, and purified with a HLB (hydrophilic lipophilic balance) cartridge. Linearity of a matrix-matched calibration curve using seven concentration levels, from 0.001 to 0.1 mg/kg, was excellent with a correlation coefficient ($R^2$) of more than 0.9998. The limits of detection (LOD) and quantification (LOQ) of instrument were 0.0005 and $0.001{\mu}g/mL$, respectively, and the LOQ of analytical method calculated as 0.01 mg/kg. The average recoveries at three spiking levels (LOQ, $LOQ{\times}10$, $LOQ{\times}50$, n=5) were in the range of 71.2~95.4% with relative standard deviation of less than 12.1%. The developed method was simple and all optimized results was satisfied with the criteria ranges requested in the Codex guidelines and Food Safety Evaluation Department guidelines. The present study could be served as a reference for the establishment of maximum residue limits (MRL) of kasugamycin and be used as basic data for safety management relative to kasugamycin residues in imported and domestic agricultural products.

Esterification of Indonesia Tropical Crop Oil by Amberlyst-15 and Property Analysis of Biodiesel (인도네시아 열대작물 오일의 Amberlyst-15 촉매 에스테르화 반응 및 바이오디젤 물성 분석)

  • Lee, Kyoung-Ho;Lim, Riky;Lee, Joon-Pyo;Lee, Jin-Suk;Kim, Deog-Keun
    • Journal of the Korean Applied Science and Technology
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    • v.36 no.1
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    • pp.324-332
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    • 2019
  • Most countries including Korea and Indonesia have strong policy for implementing biofuels like biodiesel. Shortage of the oil feedstock is the main barrier for increasing the supply of biodiesel fuel. In this study, in order to improve the stability of feedstock supply and lower the biodiesel production cost, the feasibility of biodiesel production using two types of Indonesian tropical crop oils, pressed at different harvesting times, were investigated. R. Trisperma oils, a high productive non-edible feedstocks, were investigated to produce biodiesel by esterification and transesterification because of it's high impurity and free fatty acid contents. the kindly provided oils from Indonesia were required to perform the filtering and water removal process to increase the efficiency of the esterificaton and transesterification reactions. The esterification used heterogeneous acid catalyst, Amberlyst-15. Before the reaction, the acid value of two types oil were 41, 17 mg KOH/g respectively. After the pre-esterification reaction, the acid value of oils were 3.7, 1.8 mg KOH/g respectively, the conversions were about 90%. Free fatty acid content was reduced to below 2%. Afterwards, the transesterification was performed using KOH as the base catalyst for transesterification. The prepared biodiesel showed about 93% of FAME content, and the total glycerol content was 0.43%. It did not meet the quality specification(FAME 96.5% and Total glycerol 0.24%) since the tested oils were identified to have a uncommon fatty acid, generally not found in vegetable oils, ${\alpha}$-eleostearic acid with much contents of 10.7~33.4%. So, it is required to perform the further research on reaction optimization and product purification to meet the fuel quality standards. So if the biodiesel production technology using un-utilized non-edible feedstock oils is successfully developed, stable supply of the feedstock for biodiesel production may be possible in the future.

Improvement of an Analytical Method for Methoprene in Livestock Products using LC-MS/MS (LC-MS/MS를 이용한 축산물 중 살충제 메토프렌의 잔류분석법 개선)

  • Park, Eun-Ji;Kim, Nam Young;Park, So-Ra;Lee, Jung Mi;Jung, Yong Hyun;Yoon, Hae Jung
    • Journal of Food Hygiene and Safety
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    • v.37 no.3
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    • pp.136-142
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    • 2022
  • The research aims to develop a rapid and easy analytical method for methoprene using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A simple, highly sensitive, and specific analytical method for the determination of methoprene in livestock products (beef, pork, chicken, milk, eggs, and fat) was developed. Methoprene was effectively extracted with 1% acetic acid in acetonitrile and acetone (1:1), followed by the addition of anhydrous magnesium sulfate (MgSO4) and anhydrous sodium acetate. Subsequently, the lipids in the livestock sample were extracted by freezing them at -20℃. The extracts were cleaned using MgSO4, primary secondary amine (PSA), and octadecyl (C18), which were then centrifuged to separate the supernatant. Nitrogen gas was used to evaporate the supernatant, which was then dissolved in methanol. The matrix-matched calibration curves were constructed using 8 levels (1, 2.5, 5, 10, 25, 50, 100, 150 ng/mL) and the coefficient of determination (R2) was above 0.9964. Average recoveries spiked at three levels (0.01, 0.1, and 0.5 mg/kg), and ranged from 79.5-105.1%, with relative standard deviations (RSDs) smaller than 14.2%, as required by the Codex guideline (CODEX CAC/GL 40). This study could be useful for residue safety management in livestock products.

Reinforcing Effects around Face of Soil-Tunnel by Crown & Face-Reinforcing - Large Scale Model Testing (천단 및 막장면 수평보강에 의한 토사터널 보강효과 - 실대형실험)

  • Kwon Oh-Yeob;Choi Yong-Ki;Woo Sang-Baik;Shin Jong-Ho
    • Journal of the Korean Geotechnical Society
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    • v.22 no.6
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    • pp.71-82
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    • 2006
  • One of the most popular pre-reinforcement methods of tunnel heading in cohesionless soils would be the fore-polling of grouted pipes, known as RPUM (reinforced protective umbrella method) or UAM (umbrella arch method). This technique allows safe excavation even in poor ground conditions by creating longitudinal arch parallel to the tunnel axis as the tunnel advances. Some previous studies on the reinforcing effects have been performed using numerical methods and/or laboratory-based small scale model tests. The complexity of boundary conditions imposes difficulties in representing the tunnelling procedure in laboratory tests and theoretical approaches. Full-scale study to identify reinforcing effects of the tunnel heading has rarely been carried out so far. In this study, a large scale model testing for a tunnel in granular soils was performed. Reinforcing patterns considered are four cases, Non-Reinforced, Crown-Reinforced, Crown & Face-Reinforced, and Face-Reinforced. The behavior of ground and pipes as reinforcing member were fully measured as the surcharge pressure applied. The influences of reinforcing pattern, pipe length, and face reinforcement were investigated in terms of stress and displacement. It is revealed that only the Face-Reinforced has decreased sufficiently both vertical settlement in tunnel heading and horizontal displacement on the face. Vertical stresses along the tunnel axis were concentrated in tunnel heading from the test results, so the heading should be reinforced before tunnel advancing. Most of maximum axial forces and bending moments for Crown-reinforced were measured at 0.75D from the face. Also it should be recommended that the minimum length of the pipe is more than l.0D for crown reinforcement.