• Title/Summary/Keyword: autocatalytic activation

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Cure Kinetics of a Bisphenol-A Type Vinyl-Ester Resin Using Non-Isothermal DSC

  • Ahn, WonSool
    • Elastomers and Composites
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    • v.53 no.1
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    • pp.1-5
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    • 2018
  • In the current research, the curing kinetics of a mixture system consisting of a Bisphenol-A type vinyl ester resin and styrene monomer was studied. Methylethylketone peroxide and cobalt octoate were used as the polymerization initiator and accelerator respectively. Thermograms with several different heating rates were obtained using non-isothermal differential scanning calorimetry. Activation energy values analyzed by the Flynn-Wall-Ozawa isoconversional method showed a three-step change with conversion ${\alpha}$: a slight decrease initially for ${\alpha}$ < 0.1, a constant value of 47.9 kJ/mol in the range 0.1 < ${\alpha}$ < 0.7, and a slow increase for 0.7 < ${\alpha}$. When assuming a constant activation energy of 47.9 kJ/mol, an autocatalytic model of the Sestak-Berggren equation was considered as the proper mathematical model of the conversion function, indicating an overall order of 1.2.

A Kinetic Study of Biphenyl Type Epoxy-Xylok Resin System with Different Kinds of Catalysts

  • 한승;김환근;윤호규;문탁진
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1199-1203
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    • 1997
  • The investigation of cure kinetics of biphenyl epoxy (4,4-diglycidyloxy-3,3,5,5-tetramethyl biphenyl)-xylok resin system with four different catalysts was performed by differential scanning calorimeter using an isothermal approach. All kinetic parameters of the curing reaction including the reaction order, activation energy and rate constant were calculated and reported. The results indicate that the curing reaction of the formulations using triphenylphosphine (TPP) and 1-benzyl-2-methylimidazole (1B2MI) as a catalyst proceeds through a first order kinetic mechanism, whereas that of the formulations using diazabicyloundecene (DBU) and tetraphenyl phosphonium tetraphenyl borate (TPP-TPB) proceeds by an autocatalytic kinetic mechanism. To describe the cure reaction in the latter stage, we have used the semiempirical relationship proposed by Chern and Poehlein. By combining an nth order kinetic model or an autocatalytic model with a diffusion factor, it is possible to predict the cure kinetics of each catalytic system over the whole range of conversion.

Curing Behavior of Epoxy Resins Using Aminolysis Products of Waste Polyurethanes as Hardeners

  • Lee, Dai-Soo;Hyun, Song-Won;Seo, Seung-Wook;Kim, Kyoung-Jong
    • Proceedings of the IEEK Conference
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    • 2001.10a
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    • pp.738-741
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    • 2001
  • We carried out aminolyses of various rigid polyurethane foams (PUFs) using diethylene triamine and studied application of the aminolysis products as hardners of epoxy resins. Diglycidyl ether of bisphenol A was used for the study on the curing behavior of epoxy resin with the aminolysis product employing differential scanning calorimeter. Curing reaction of the epoxy resin is generally known to be autocatalytic second order reaction. We found that the curing reaction of the epoxy resin with the aminolysis product of rigid PUF did not show autocatalytic characteristics but followed the n-th order kinetics. The activation energy of the curing reaction of the epoxy resin with the aminolysis product of rigid PUF made from sugar based polyol was slightly lower than that of the epoxy resin with aminolysis product of rigid with made from amine based polyol.

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Study on Cure Behavior of Low Temperature and Fast Cure Epoxy with Mercaptan Hardener (Mercaptan 경화제에 의한 저온속경화 에폭시의 경화거동에 관한 연구)

  • Eom, Se Yeon;Seo, Sang Bum;Lee, Kee Yoon
    • Polymer(Korea)
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    • v.37 no.2
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    • pp.240-248
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    • 2013
  • The curing behaviors of diglycidyl ether of bisphenol A (DGEBA) with mercaptan hardener were studied by the comparison with amine-adduct type hardener. Curing behaviors were evaluated by DSC at dynamic and isothermal conditions. In the DSC, the dynamic experiments were based on the method of Kissinger's equation, and the isothermal experiments were fitted to the Kamal's kinetic model. Activation energy of epoxy/amine-adduct type hardener was ca. 40 kcal/mol. As the functional group of mercaptan hardener, -SH increased, on epoxy/mercaptan hardeners, the activation energies decreased from 28 to 19 kcal/mol. Epoxy/amine-adduct type hardener was initiated at $90^{\circ}C$ or higher. However, epoxy/mercaptan hardeners reduced the initiation temperatures below $80^{\circ}C$ and shortened the durations of curing reaction within 10 min. We found out that the reaction kinetics of epoxy with mercaptan hardener followed the autocatalytic reaction models, and the maximum reaction rates were shown at the conversions of 20~40%.

Preparation of Quaternary Energetic Composites by Crystallization and Their Thermal Decomposition Characteristics (결정화에 의한 4성분계 에너지 복합체 제조 및 열분해 특성)

  • Kim, Byoung-Soo;Kim, Jae-Kyeong;Ahn, Ik-Sung;Kim, Hyoun-Soo;Koo, Kee-Kahb
    • Applied Chemistry for Engineering
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    • v.30 no.2
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    • pp.178-185
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    • 2019
  • Three spherical quaternary composites composed of metal/metal oxide/high explosive/oxidizer were prepared by a crystallization/agglomeration process. From the characteristics of composites by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), the shortening of the decomposition zone of high explosives in the quaternary composite was observed, which may be attributed to the autocatalytic reaction caused by $ClO_2$ or HCl which are ammonium perchlorate (AP) degradation products. The activation energy analysis showed that the activation energy abruptly decreases at the end of the decomposition zone of high explosives, and it was considered to be caused by $HNO_2$ which is common in decomposition products of high explosives. The activation energy predicted from complex pyrolysis results by the distributed activation energy model (DAEM) showed much better in accuracy than those by model-fitting methods such as Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa models.

The effect of hexamethylenetetramine contents and cure properties on friction characteristics of phenolic resin (페놀수지의 마찰특성에 미치는 HEXA의 함량 및 경화도의 영향)

  • Kim, Dae-Kyeun;Jang, Ho;Yoon, Ho-Gyu
    • Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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    • 1999.11a
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    • pp.49-56
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    • 1999
  • A material was formulated with Phenol novolac and HEXA only. The cure kinetics and thermal characteristics of phenol novolac with various HEXA contents were peformed by differential scanning calorimetry and thermal gravimetric analysis. All kinetic parameters of the curing reaction including the reaction order, activation energy, and rate constant were calculated and reported. The results indicate that the curing reaction goes through an autocatalytic kinetic mechanism. The friction and wear characteristics of this material were determined using friction material testing machine. The friction coefficient of phenol novolac with various HEXA contents was determined using the PV(pressure & velocity) factor. The most stable and highest friction coefficient with a various pressure and velocity condition was found at HEXA 10 wt.% material. The specific wear rate per unit sliding distance with a various HEXA contents was reported.

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Alteration of Substrate Specificity of Achromobacter Protease l (API) (Achrobacter Protease I (API)의 기질특이성의 전환)

  • Lim, Seong-Il;Choi, Cheong
    • Applied Biological Chemistry
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    • v.40 no.3
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    • pp.196-201
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    • 1997
  • Assuming that Asp225 is the substrate specificity determinant of Achromobacter pretense I (APl) which is lysine-specific serine protease, the 225th residue was substituted for other amino acids with a hope that the substrate specificity of a mutant API is altered. Furthermore, to maturate preform of mutant API autocatalytically, Lys(-1) was also replaced by Met, Asp, or Glu. However, all the mutants were not expressed, or accumulated as inactive precursor proteins. This result implicats that Asp225 plays a critical rol in restricted substrate specificity as a lysylendopeptidase but the substrate specificity of API is not determined only by the nature of residue 225.

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Cure Kinetics of amine-cured tetraglycidyl-4,4'-diaminodiphenylmethane epoxy blends with a new polyetherimide (반응성 열가소성 수지로 개질된 TGDDM/DDS 시스템의 Cure Kinetics)

  • Hwang Seungchul;Lee JungHoon;Kim Donghyon;Kim Woho;Kim Minyoung
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2004.04a
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    • pp.214-217
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    • 2004
  • The cure kinetics of blends of epoxy(tetraglycidyl-4,4'-diaminodiphenylmethane ; TGDDM)/curing agent(diaminodiphenyl sulfone ; DDS) resin with amine terminated polyetherimide-CTBN-amine terminated polyetherimide triblock copolymer(ABA) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction parameters such as activation energy and reaction constants. By increasing the amount of ABA in the blends, the final cure conversion was decreased. Lower values of the final cure conversions in the epoxy/ABA blends indicated that ABA hinders the cure reaction between the epoxy and curing agents. 1be value of the reaction order, m, for the initial autocatlytic reaction was not affected by blending ABA with epoxy resin, and the value was approximately 1.0. The value of n for the nth order component in the autocatalytic analysis was increased by increasing the amount of ABA in the blends, and the value increased from 2.0-3.4. A diffusion controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/DDS/ABA blends.

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Cure Kinetics and Dynamic Mechanical Properties of an Epoxy/Polyoxypropylene Diamine System (에폭시/폴리옥시프로필렌 디아민계의 경화 반응속도 및 동역학 특성 분석)

  • Huang, Guang-Chun;Lee, Jong-Keun
    • Polymer(Korea)
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    • v.35 no.3
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    • pp.196-202
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    • 2011
  • The cure kinetics of a bisphenol A epoxy resin and polyoxypropylene diamine curing agent system are investigated in both dynamic and isothermal conditions by differential scanning calorimetry (DSC). In dynamic experiments, the shift of exothermic peaks obtained at different heating rates is used to obtain activation energy of overall cure reaction based on the methods of Ozawa and Kissinger. Isothermal DSC data at different temperatures are fitted to an autocatalytic Kamal kinetic model. The kinetic model is in a good agreement with the experimental data in the initial stage of cure. A diffusion effect is incorporated to describe the later stage of cure, predicting the cure kinetics over the whole range of curing process. Also, dynamic mechanical analysis is performed to evaluate the storage modulus and average molecular weight between crosslinkages.

Changes in flavor-relevant compounds during vine ripening of tomato fruit and their relationship with ethylene production

  • Wang, Libin;Luo, Weiqi;Sun, Xiuxiu;Qian, Chunlu
    • Horticulture, Environment, and Biotechnology : HEB
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    • v.59 no.6
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    • pp.787-804
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    • 2018
  • Flavor quality is import for determining consumer perception and acceptance of tomato products. In this study, 'Fendou' tomato fruit were harvested at six ripening stages and sampled to investigate the development of flavor-relevant compounds during vine ripening. Results showed that upon the initiation of ripening there was an increase in respiration rate and concomitant ethylene evolution that was associated with increased membrane permeability. In accordance with these physiological changes, flavor-relevant compounds demonstrated different expression patterns as fruit ripened, which contributed to 'red-ripe' flavor characteristics of red-ripe fruit. Based on correlation analysis between ethylene evolution and the flavor-relevant compounds during 'Fendou' tomato ripening and the other researchers' reports, the activation of System 2-dependent autocatalytic ethylene production plays an important role in the development of most flavor-relevant compounds during tomato vine ripening. Overall, our results suggested that most flavor-relevant compounds that accumulated the most during tomato fruit ripening at red stage could be under ethylene regulation and were among the most important contributors to the 'red-ripe' flavor. Due to the development of these compounds, the flavor quality at late ripening stages is different from that of fruit at early ripening stages.