• Journal of the Korean Wood Science and Technology
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• 제47권4호
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• pp.442-450
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• 2019

Despite its potential as a renewable source for fuels and chemicals, lignin valorization still faces technical challenges in many aspects. Overcoming such challenges associated with the chemical recalcitrance of lignin can provide many opportunities to innovate existing and emerging biorefineries. In this work, we leveraged a biomass genetic engineering technology to produce phenolic aldehyde-rich lignin structure via downregulation of cinnamyl alcohol dehydrogenase (CAD). The structurally altered lignin obtained from the Arabidopsis thaliana CAD mutant was pyrolyzed to understand the effect of structural alteration on thermal behavior of lignin. The pyrolysis was conducted at 400 and $500^{\circ}C$ using an analytical pyrolyzer connected with GC/MS and the products were systematically analyzed. The results indicate that aldehyde-rich lignin undergoes fragmentation reaction during pyrolysis forming a considerable amount of C6 units. Also, it was speculated that highly reactive phenolic aldehydes facilitate secondary repolymerization reaction as described by the lower yield of overall phenolic compounds compared to wild type (WT) lignin. Quantum mechanical calculation clearly shows the higher electrophilicity of transgenic lignin than that of WT, which could promote both fragmentation and recondensation reactions. This work provides mechanistic insights toward biomass genetic engineering and its application to the pyrolysis allowing to establish sustainable biorefinery in the future.

• Macromolecular Research
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• 제15권6호
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• pp.565-574
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• 2007

In this study, five representative, commercially available polymers, Ultem 1000 polyetherimide, Kapton polyimide, phenolic resin, polyacrylonitrile and cellulose acetate, were used to prepare pyrolyzed polymer membranes coated on a porous {\alpha}-alumina$ tube via inert pyrolysis for gas separation. Pyrolysis conditions (i.e., final temperature and thermal dwell time) of each polymer were determined using a thermogravimetric method coupled with real-time mass spectroscopy. The surface area and pore size distribution of the pyrolyzed materials derived from the polymers were estimated from the nitrogen adsorption/desorption isotherms. Pyrolyzed membranes from polymer precursors exhibited type I sorption behavior except cellulose acetate (type IV). The gas permeation of the carbon/{\alpha}-alumina$ tubular membranes was characterized using four gases: helium, carbon dioxide, oxygen and nitrogen. The polyetherimide, polyimide, and phenolic resin pyrolyzed polymer membranes showed typical molecular sieving gas permeation behavior, while membranes from polyacrylonitrile and cellulose acetate exhibited intermediate behavior between Knudsen diffusion and molecular sieving. Pyrolyzed membranes with molecular sieving behavior (e.g., polyetherimide, polyimide, and phenolic resin) had a $CO_2/N_2$ selectivity of greater than 15; however, the membranes from polyacrylonitrile and cellulose acetate with intermediate gas transport behavior had a selectivity slightly greater than unity due to their large pore size.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1276-1280
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• 2003

Thermal behavior of bromphenols was investigated by direct pyrolysis at high temperature. The thermal degradation products formed by the pyrolysis of mono-bromophenols (o-, m-, and p-) were identified by gas chromatography-mass spectrometry. During the pyrolysis reactions, several kinds of dioxins and furans were produced, and the relative ratio of pyro-products was dependent on the substituted position of bromine in phenolic structure due to the effect of symmetry and steric hindrance. The formation of dioxins can be explained by the phenoxy radical addition and Br atom elimination at an ortho-carbon site on phenolic structure. On the other hand, the formation of furans can be explained by the ortho-ortho carbon coupling of phenoxy radicals at unsubstituted sites to form o, o'-dihydroxydiphenyl intermediate via its keto-tautomer, followed by $H_2O$ elimination. The pyrolysis temperature has also a substantial effect on the dimerized products quantities but little effect on the type of pyro-products. Moreover, the formation mechanism of pyro-products was suggested on the basis of products identified.

• Environmental Engineering Research
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• 제21권2호
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• pp.180-187
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• 2016

In the present work, bael shell (aegle marmelos) is used as the feedstock for pyrolysis, using a fixed bed reactor to investigate the characteristics of the pyrolysis oil. The product yields, e.g., liquid, char and gases are produced from the biomass at different temperatures with the particle size of 0.5-1.0 mm, at the heating rate of $150^{\circ}C/min$. The maximum liquid yield, i.e., 36.23 wt.%, was found at $5500^{\circ}C$. Some physical properties of the pyrolysis oil such as calorific value, viscosity, density, pH, flash point and fire point are evaluated. The calorific value of the bael shell pyrolysis oil was 20.4 MJ/kg, which is slightly higher than the biomass, i.e., 18.24 MJ/kg. The H/C and O/C ratios of the bio-oil were found as 2.3 and 0.56 respectively, which are quite higher than some other bio-oils. Gas Chromatography and Mass Spectroscopy (GC-MS) and Fourier Transform Infra-red (FTIR) analyses showed that the pyrolysis oil of bael shell is mostly composed by phenolic and acidic compounds. The results of the properties of the bael shell pyrolysis oil reveal the potential of the oil as an alternate fuel with the essential upgradation of some properties.

• 한국세라믹학회지
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• 제36권5호
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• pp.513-520
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• 1999

Alumina-coated SiC whiskers wee prepared by the calcination (1150$^{\circ}C$, 1h, Ar) of the alumina hydrate layer which was precipitated homogeneously on whisker surface from a solution of Al2(SO4)3 and urea as a precipitant. In addition carbon coated SiC whiskers were prepared by the pyrolysis (1000$^{\circ}C$, 4h Ar) of phenolic resin coated whisker. The effects of coating conditions on the thickness and morphology of the coated layers were examined by SEM and TEM. It was found that Al2O3-coating layers become thinner and more uniform with decreasing the Al2(SO4)3 concentration. Thin (0.075-0.1$\mu\textrm{m}$) and uniformly alumina-coating layers were obtained at the Al2(SO4)3 concentration 0.010mol/l. On the other han carbon-coating layers were uniform but very thin (5-16 nm) in thickness. For thicker carbon-coating layers ethanol as a disperse medium was found to be more efficient compared tousing acetone.

• 한국항공우주학회지
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• 제39권8호
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• pp.711-718
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• 2011

본 논문에서는 열화학적 분해 및 열기계학적 변형이 고려된 구성 방정식을 사용하여 다공성 탄소/페놀릭 복합재료의 열탄성 거동을 예측하였다. 다공성 복합재료의 온도 의존성 및 열화학적 분해 과정에서의 기공도, 분해 가스에 의한 기공 압력, 재료의 수축을 고려하였다. 기공도와 기공 압력이 고려된 대표 체적 요소 모델의 유한요소 해석을 통해 산출된 거시적 기공 탄성 계수를 구성 방정식에 적용하였다. 간단한 수치 실험을 통해 기공탄성 계수가 다공성 재료의 열탄성 거동에 미치는 영향을 분석하였으며, 재료 내부에 형성된 기공과 기공 압력에 의한 응력 구배 및 변형을 확인하였다.

• 한국항공우주학회지
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• 제49권5호
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• pp.355-363
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• 2021

리오셀계 탄소/페놀릭 복합재료의 항공우주용 내열 부품 적용 가능성을 확인하기 위하여 내열성능 평가 및 열 해석을 수행하였다. 탄소/페놀릭의 열반응 평가는 내열성능평가모터(Thermal Protection Evaluation Motor, TPEM)로 수행되었다. 본 논문에서는 열 해석을 위해 유체의 경계층 해석을 고려한 경계층 적분 코드와 삭마 및 열분해를 고려한 MSC-Marc 2018 코드를 사용하였다. 추진기관의 압력 곡선, 연소 시험 후 절개된 목삽입재 시편을 통하여 삭마 및 단열성능을 분석하였고, 리오셀계 탄소/페놀릭 복합재료의 열반응은 레이온계 탄소/페놀릭 재료와 유사하였다. 연소시험을 통한 결과를 바탕으로 국산 리오셀계 탄소/페놀릭의 항공우주용 내열 부품으로의 적용 가능성을 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.811-814
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• 2014

Bio-oil instability, or aging, is a significant problem for the long-term storage of fast pyrolysis oils. We investigated bio-oil aging at the molecular level using Fourier-transform ion cyclotron resonance mass spectrometry. Petroleomic analysis suggests that bio-oil aging is resulted from the oligomerization of phenolic lignin products whereas 'sugaric' cellulose/hemicellulose products have negligible effect.

• 한국항공우주학회지
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• 제41권8호
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• pp.597-604
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• 2013

본 논문에서는 열분해 및 삭마 환경의 복합재 구조물에 대한 열기계적 연계 해석을 수행하였다. 열분해 과정의 재료 밀도 감소, 기공 가스 확산, 흡열 반응 에너지와 삭마 과정에서의 표면 침식 효과 등을 고려하였다. 상용 유한요소 코드에 교차 연계 알고리듬을 적용하여 완전 연계된 열 해석 및 구조 해석 인터페이스를 구성하였다. 수치 실험을 통해서 탄소/페놀릭 복합재료의 기본적인 열분해 및 삭마 특성을 분석하였다. 특히, 화학적 및 기계적 삭마에 영향을 미치는 주요 인자에 따른 표면 침식량 등을 비교하였다. 또한, 열분해 과정의 수축 또는 팽창 변형도가 재료의 열기계적 거동에 미치는 영향도 검토하였다.

• 한국연초학회지
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• 제22권2호
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• pp.176-183
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• 2000

This study was conducted to compare the volatile components of lamina(cutter group) and midrib of flue-cured tobacco leaves by two analytical methods, Curie-Point pyrolysis and Purge & Trap headspace technique. The pyrolysis of lamina and midrib part of tobacco leaves was performed at the temperature of $330^{\circ}C$, $650^{\circ}C$, and $920^{\circ}C$ by Curie-Point Pyrolyzer, and 33 compounds were identified in the pyrolyzates by GC/MSD. The composition of the components identified showed a quite difference between lamina and midrib. However, the amount of the pyrolyzed products from the both of lamina and midrib was increased with temperature increase except that of acetic acid, furfural, and nicotine. The content of phenolic compounds including phenol, 4-methyl phenol, and 3-methyl phenol was higher in midrib than in lamina, while that of furan compounds such as 2,3-dihydrobenzofuran, 5-hydroxymethyl furfural, was high in lamina. Interestingly, acetamide, 2-propenamide and 3-acetoxy pyridine were not defected in the pyrolyzates of lamina. By Purge & Trap headspace technique, 28 volatile components were identified in both lamina and midrib. The composition of the identified compounds and their chromatograpic patterns also showed the complete difference between the two. The content of solanone, $\beta$-damascone, $\beta$-damascenone, and megastigmatrienones, key components of tobacco aroma, was much higher in lamina than in midrib. The results indicate that lamina contains much more carbonyl compounds known to enhance the smoke taste of cigarette, whereas midrib takes nitrogenous and phenolic compounds, which are known to cause a deteriorate effect of smoke such as irritation.