• Macromolecular Research
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• 제12권5호
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• pp.466-473
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• 2004

We have used FT-IR spectra to explain the effects of hydrogen bonding between chitosan and polycaprolactam (PA6). A dynamic mechanical analysis study suggested that the optimum chitosan and PA6 miscibility under the conditions of this experiment were obtained at a blending ratio of 40:60. We studied the thermal degradation of chitosan blended with PA6 (chitosan/PA6) by thermogravimetric analysis and kinetic analysis (by the Ozawa method). Dry chitosan and PA6 exhibited a single stage of thermal degradation and chitosan/PA6 blends having> 20 wt% PA6 exhibited at least two stages of degradation. In chitosan/PA6 blends, chitosan underwent the first stage of thermal degradation; the second stage proceeded at a temperature lower than that of PA6, because the decomposition product of chitosan accelerated the degradation of PA6. The activation energies of the blends were between 130 and 165 kJ/mol, which are also lower than that of PA6.

• 대한안전경영과학회지
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• 제10권4호
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• pp.111-120
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• 2008

The combustion reaction of polypropylene was investigated using a thermogravimetric technique under an air atmosphere condition at several heating rates from 10 to $50^{\circ}C/min$. To obtain information on the kinetic parameters, the dynamic thermogravimetric analysis curve and its derivative were analyzed by a variety of analytical methods such as Kissinger, Friedman, Freeman-Carroll, Chatterjee-Conrad, Ozawa and Coats-Redfern methods. The comparative works for the kinetic results obtained from various methods should be performed to determine the kinetic parameters, because there are tremendous differences in the calculated kinetic parameters depending upon the mathematical method taken in the analysis.

• Elastomers and Composites
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• 제23권3호
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• pp.213-222
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• 1988

The thermal decomposition of poly(n-butyl methacrylate)(Pn-BMA) was studied using a dynamic and isothermal thermogravimetry in nitrogen gas with 50ml/min at several heating rates from 1 to $20^{\circ}C/min$, and at several heating temperature from 320 to $370^{\circ}C$. The mathematical techniques used for calculation of activation energy were Kissinger, Anderson, Chatterjee-Conrad, Friedman, Fuoss, Ozawa and isolthermal method. The range of activation energies obtained using the several techniques was between 43 and 51Kcal/mol except Chatterjee-Conrad and this range agreed with each other very well. The thermal degradation of Pn-BMA was considered to be carried out by main chain scission.

• 환경위생공학
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• 제15권4호
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• pp.123-133
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• 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.

• Korean Chemical Engineering Research
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• 제54권3호
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• pp.404-409
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• 2016

비등온의 열중량분석기(TGA)에 의해 nitrate-citrate 혼합물의 전구체로부터 $LaMnO_3$ 합성반응의 열적특성과 반응특성을 고찰하였다. TGA의 승온속도는 5.0, 10.0, 15.0, 20.0 K/min으로 조정하였다. $LaMnO_3$ 합성반응은 승온속도의 변화에 따라 450~600 K (X=0.4~0.7)에서 빠르게 진행되었다. $LaMnO_3$ 합성반응의 활성화에너지는 Friedman, Ozawa-Flynn-Wall 그리고 Vyazovkin의 방법으로 해석하였는데, 반응전환율의 변화에 따라 23~243 kJ/g-mol 범위 값을 나타내었다. 반응차수는 승온속도와 반응전환율이 증가함에 따라 감소하였다. 반응차수의 평균값은 반응전환율이 0.1~0.3의 범위인 반응초기에는 4.5이었으며, 반응전환율이 0.7~0.9 범위인 반응의 종결 부분에서는 1.87이었다. 반응속도의 빈도인자는 승온속도와 반응전환율의 증가에 따라 점차 증가하였다. 반응속도의 빈도인자(frequency factor)는 반응전환율이 0.1~0.3인 경우에는 205.6 ($min^{-1}$)이었으며 반응전환율이 0.7~0.9인 경우에는 475.2 ($min^{-1}$)이었다.

• 공업화학
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• 제28권1호
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• pp.23-28
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• 2017

열중량 분석기와 파이롤라이저-가스크로마토그래피/질량분석기를 이용하여 폐플라스틱 필름의 열분해 특성연구를 수행하였다. 열중량 분석 결과, 최근 사용량이 증가된 녹말 첨가 바이오 플라스틱의 영향으로 폐플라스틱 필름의 열분해는 $200^{\circ}C$에서 $370^{\circ}C$ 사이의 녹말 분해구간과 $370^{\circ}C$에서 $510^{\circ}C$ 사이의 PS, PP, PE와 같은 플라스틱계열의 고분자 분해구간을 가지는 것을 확인할 수 있었다. Revised Ozawa method를 이용한 동역학 분석 결과 폐플라스틱 필름의 열분해 반응 활성화 에너지는 녹말과 플라스틱계열 고분자의 다른 분해 반응에 의해 급격하게 변화되었다. 파이롤라이저-가스크로마토그래피/질량분석 결과 폐플라스틱 필름에 포함된 각 고분자의 열분해 부산물인 levoglucosan (녹말), terephthalic acid (PET), styrene monomer/dimer/trimer (PS), methylated alkenes (PP), alkadiene/alkene/alkane으로 구성된 triplet 피크 (PE)가 나타남을 확인할 수 있었다. 또한 고분자 첨가제로 사용되는 프탈레이트 성분도 검출되었다.

• Korean Chemical Engineering Research
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• 제45권6호
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• pp.604-610
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• 2007

납사타르피치의 연소 및 수증기 가스화의 반응특성을 알아보기 위하여 납사타르피치를 탄소원으로 사용하여 열중량분석을 수행하였다. 반응의 활성화에너지, 반응차수, 빈도인자 등을 구하기 위하여 Friedman 방법과 Ozawa-Flynn-Wall 방법이 사용되었다. Friedman 방법을 사용하여 반응전환에 따른 연소의 활성화에너지를 구하였는데, 0.2~0.6 정도의 전환이 일어났을 때는 활성화에너지가 41.6~68.1 kJ/g-mol이었다. 0.9~1.0 정도의 전환이 일어났을 때는 183.1~191.2kJ/g-mol이었다. 그리고 수증기 가스화에 대해서는, 0.2~0.6 반응전환에서 활성화에너지는 31.9~44.9 kJ/g-mol이었다. 0.8~0.95 전환에서는 70.6~87.8 kJ/g-mol이었다. 이러한 결과로 미루어보아 반응은 탈휘발화와 연소 또는 가스화 반응의 두 단계로 진행되는 것을 알 수 있었다.

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

• 한국세라믹학회지
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• 제53권1호
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• pp.24-33
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• 2016

The grafting reaction for maleic anhydride (MA) onto high density polyethylene (HDPE) was investigated from solution process with initiators. The chemical modification of neat HDPE was carried out with various contents of MA (3-21 wt.%) and initiator (0.2-1 wt.%) at different temperature ($80-130^{\circ}C$). The grafting degree was obtained from the titration and the highest grafting degree was 3.1%. The grafting degree increased as the content of MA and initiator increased, however, the highest grafting degree was demonstrated for a particular content of MA and initiator. In the non-isothermal crystallization kinetics, the Ozawa model was unsuitable method to investigate the crystallization behavior of MA onto HDPE, whereas the Avrami and Liu models found effective. The crystallization rate was accelerated as the cooling rate increased, but postponed by combination of MA onto neat HDPE backbone.

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