• 환경위생공학
• /
• 제15권4호
• /
• pp.123-133
• /
• 2000

The kinetic analysis was carried out for commercial rubbers such as NR, IR, BR, SBR 1500, and SBR 1700. Kinetic analysis for the commercial rubbers was performed using the thermogravimetric method, with which the activation energies of NR obtained by Kissinger, Friedman, and Ozawa's method were 195.0, 198.3 and 186.3kJ/mol, whereas that of SBR 1500 were 246.4, 247.5 and 254.8kJ/mol, respectively. It was shown that the yield of pyrolytic oil was generally increased with final temperature increasing, yet slightly decreased or increased over $700^{\circ}C$. Considering the effect of heating rate, it was found that the yield of pyrolytic oil was not consistent for each sample. The number average molecular weight of SBR 1500 was in the range of 740~2486. The calorific value of SBR 1500 was 39~40kJ/g, which were made comparative study of the conventional fuel such as kerosene, diesel, light fuel, and heavy fuel. Therefore it was essential that the selection of the suitable kinetic model and the mathematical solution because of the difference in parameters obtained from each method. It was proposed that the range of $600~700^{\circ}C$ in final temperature and high heating rate due to short run time. It was suggested that the pyrolytic oil be available to use to the fuel.

• 한국안전학회지
• /
• 제18권3호
• /
• pp.81-87
• /
• 2003

Latex polymers are widely used for adhesive, binder, paint etc. Especially the PVAc(Polyvinyl acetate) latex which manufactured by vinyl acetate and vinyl alcohol as protective colloid is a useful environmentally friendly adhesive. To increase useful property of PVAc latex, this study was carried out for checking thermal characteristics and physical condition of PVAc latex by DSC, FT-IR, Pyrolyzer GC-MS. The activation energies of thermal decomposition for 40, 48, 56, 64% solid content of PVAc latex were found as 28.1-36.0kcal/mol by Kissinger's method and 17.2-22.0kcal/mol by DSC method. Actually, reasonable solid content could be consiered as 56% because of activation energy and adhesive characteristics. According to the effect of protective colloid for 4, 10, 15, 20wt%, the activation energy shows same tendency to both method and in case of l5wt% has been found as the highest activation energy. The mechanism of thermal decomposition was mainly estimated by main chain scission, not by side group on FT-IR analysis. Main component of Pyrolzer GC-MS result were consisted of $CH_3COOH$, $CH_3$, $H_2O$ and light gases(CO, $CO_2$, $CH_4$ etc).

• Macromolecular Research
• /
• 제14권5호
• /
• pp.491-498
• /
• 2006

The thermal degradation of poly(hexamethylene guanidine) phosphate (PHMG) was studied by dynamic thermogravimetric analysis (TGA) and pyrolysis-GC/MS (p-GC). Thermal degradation of PHMG occurs in three different processes, such as dephosphorylation, sublimation/vaporization of amine compounds and decomposition/ recombination of hydrocarbon residues. The kinetic parameters of each stage were calculated from the Kissinger, Friedman and Flynn-Wall-Ozawa methods. The Chang method was also used for comparison study. To investigate the degradation mechanisms of the three different stages, the Coats-Redfern and the Phadnis-Deshpande methods were employed. The probable degradation mechanism for the first stage was a nucleation and growth mechanism, $A_n$ type. However, a power law and a diffusion mechanism, $D_n$ type, were operated for the second degradation stage, whereas a nucleation and growth mechanism, $A_n$ type, were operated again for the third degradation stage of PHMG. The theoretical weight loss against temperature curves, calculated by the estimated kinetic parameters, well fit the experimental data, thereby confirming the validity of the analysis method used in this work. The life-time predicted from the kinetic equation is a valuable guide for the thermal processing of PHMG.

• 한국추진공학회지
• /
• 제14권6호
• /
• pp.31-37
• /
• 2010

본 연구에서는 Hydroxyl Terminated Polyether(HTPE) 추진제 원료 및 HTPE 둔감 추진제 조성 2종에 대하여 Differential Scanning Calorimetry(DSC)와 Thermal Gravimetric Analysis(TGA)를 사용하여 열분해 특성을 고찰하였고, EIDS 완속가열 시험을 수행하였다. AN이 포함된 HTPE 002는 약 $125^{\circ}C$에서 AN의 상전이과정(II$\rightarrow$I)을 거친 후, 약 $200^{\circ}C$범위까지 BuNENA와 AN이 함께 발열특성을 가지고 분해됨을 알 수 있었다. EIDS 완속가열 시험을 수행한 결과 HTPE 001은 $250^{\circ}C$, HTPE 002는 $152^{\circ}C$ 부근에서 반응이 있어났으며, 두 추진제 모두 $115^{\circ}C$부근에서 급격한 온도 상승이 일어났다. 추진제 HTPE 001과 HTPE 002의 열폭발에 대한 임계온도, Tc,를 Semenov의 열폭발 이론과 몇 가지 가열속도에서 측정된 비등온 곡선으로부터 계산되었고, 임계온도 계산에 사용된 열분해에 대한 활성화에너지는 Kissinger 방법으로 측정하였다.

• Korean Chemical Engineering Research
• /
• 제49권1호
• /
• pp.114-119
• /
• 2011

인도네시아 아역청탄인 ABK탄과 중국 갈탄(lignite)과 같은 저급탄에 대한 열분해와 촤-$CO_2$ 가스화반응에 대한 실험을 비등온의 승온 조건에서 열중량분석기(Thermogravimetric analysis, TGA)를 이용하여 수행하였다. 열분해 속도는 2단계, 1차의 열분해 모델(Kissinger 법의 변형)에 의해 잘 모사되었다. 촤의 $CO_2$ 가스화반응은 수축 핵 모델에 적용하여 초기의 활성화 에너지가 ABK탄은 189.1 kJ/mol, lignite는 260.5 kJ/mol의 값을 얻었으며, 수축 핵 모델에 의해 잘 모사되었다. 특히, 촤의 $CO_2$ 가스화반응에서 활성화 에너지는 무연탄의 결과와 유사하였으며, 다른 모델이나 석탄의 종류에 따라 큰 차이를 보였다.

• 폴리머
• /
• 제36권2호
• /
• pp.245-250
• /
• 2012

장쇄분지(long chain branch, LCB)를 가지는 분지화된 폴리프로필렌(polypropylene, PP)이 세 종류의 분지제(branching agent)를 이용하여 고상(solid state)에서 제조하였다. 분지화된 PP의 화학구조, 비등온결정화 거동 및 복합점도를 적외선분광기(FTIR), 시차주사열용량분석기(DSC), 광학현미경 그리고 동적유변측정기(ARES)를 이용하여 관찰하였다. 분지화된 PP의 화학구조는 3100 $cm^{-1}$에서 나타나는 분지제의 =C-H 신축진동을 이용하여 확인하였다. PP-D-0-3과 PP-F-0-3의 경우 순수 PP와 비교하여 용융온도에 큰 변화를 보이지 않은 반면 HQ를 사용한 경우에는 용융온도의 감소를 나타내었다. 이는 분지화 반응보다 분해반응이 우세하여 나타나는 현상으로 해석되고, 복합점도의 감소를 통해 확인하였다. 분지화된 PP의 비등온결정화 거동은 Avrami 방정식을 이용하여 분석하였다. PP의 Avrami 지수는 3의 값을 나타내었고, DVB와 FS로 처리된 분지화 PP의 경우는 3보다 약간 작은 값을 나타내었다. Kissinger 방법에 의해서 계산된 분지화 PP의 활성화에너지는 순수 PP의 25 kJ/mol과 큰 차이를 보이지 않았다.

• 세라미스트
• /
• 제10권3호
• /
• pp.67-74
• /
• 2007

Crystallisation kinetics of the erbium doped soda-tellurite glasses were studied using the differential thermal analysis (DTA) and differential scanning calorimetery (DSC) techniques. The DTA curves in the temperature range of 350 K to 650 K were obtained from isochronal heating rates, chosen in the range of 2 to 20 K/min. DSC isothermal curves were used to calculate the fraction of crystals formed on reheating. The apparent activation energies for devitrification were derived by measuring the shifts in the values of $T_g$ and $T_x$ with heating rates, using the Kissinger method. The derived values of apparent activation energies for isochronal and isothermal methods varied in the range of $190-204\;{\pm}\;5\;kJ\;mol^{-1}$. The X-ray powder diffraction analysis of heat treated and transparent samples showed the presence of nano-scale size sodium-tellurite crystals. These crystallites were found to have a strong influence on the full width of half maxima of the transition in $Er^{3+}:\;^4I_{13/2}{\rightarrow}^4I_{15/2}$, which extended from 70 nm in the vitreous materials to 132 nm in glass-ceramic materials.

• 한국분말재료학회지
• /
• 제16권4호
• /
• pp.262-267
• /
• 2009

Disk type porous nickel membrane was fabricated by in-situ reduction/sintering process using compacted NiO/PMMA (PMMA; Polymethyl methacrylate) mixture at $800^{\circ}C$ in hydrogen atmosphere. The porosity (49$\sim$58%) of these membrane was investigated as an amount of PMMA additive. The thermal decomposition and reduction behavior of NiO/PMMA were analyzed by TG/DTA in hydrogen atmosphere and the activation energy for the hydrogen reduction of NiO and thermal degradation of PMMA was calculated as 61.1 kJ/mol, evaluated by Kissinger method. Finally, the filtering performance and pressure drop were measured by particle counting system.

• Carbon letters
• /
• 제12권4호
• /
• pp.229-235
• /
• 2011

Isotactic polyacrylonitrile (PAN) with triad isotacticity of 0.53, which was determined by $^{13}C$ NMR, using dialkylmagnesium as an initiator, was successfully synthesized. Isothermal treatment of iso-PAN was conducted in air at 200, 220, 250 and $280^{\circ}C$. Structural evolutions and chemical changes were studied with Fourier transformation infrared and wide-angle X-ray diffraction during stabilization. A new parameter $CNF={I_{2240cm}}^{-1}/ ({I_{1595cm}}^{-1}+f^*{I_{1595cm}}^{-1})$ was defined to evaluate residual nitrile groups. Crystallinity and crystal size were calculated with X-ray diffraction dates. The results indicated that the nitrile groups had partly converted into a ladder structure as stabilization proceeded. The rate of reaction increased with treatment temperature; crystallinity and crystal size decreased proportionally to pyrolysis temperature. The iso-conversional method coupled with the Kissinger and Flynn-Wall-Ozawa methods were used to determine kinetic parameters via differential scanning calorimetry analysis with different heating rates. The active energy of the reaction was 171.1 and 169.1 kJ/mol, calculated with the two methods respectively and implied the sensitivity of the reaction with temperature.

• 한국표면공학회지
• /
• 제41권6호
• /
• pp.301-307
• /
• 2008

In this paper, nanocrystallization of CuNiTiZr bulk metallic glass (BMG) subjecting to a kinetic spraying, dependent on impact velocity, was investigated by numerical and experimental approaches. The crystallization fraction and nucleation activation energy of initial feedstock and as-deposited coating were estimated by DSC and Kissinger method, respectively. The results of numerical modeling and experiment showed that the crystalline fraction and nucleation activation energy in BMG coatings were depended on kinetic energy of incident particle. Upon impact, the conversion of particle kinetic energy leads to not only decreasing free energy barrier but also increasing the driving force for an amorphous to crystalline phase transformation. The nanocrystallization of BMGs is associated with the strain energy delivered by a plastic deformation with a high strain rate.