• Title/Summary/Keyword: Kinetics parameters

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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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Kinetics of Acrylamide Solution Polymerization Using Potassium Persulfate as an Initiator by in situ IR

  • Kang, Shin-Choon;Park, Yoo-Jeong;Kim, Hyung-Zip;Kyong, Jin-Burm;Kim, Dong-Kook
    • Macromolecular Research
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    • v.12 no.1
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    • pp.107-111
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    • 2004
  • We have studied the polymerization kinetics of acrylamide in aqueous solution with potassium persulfate as an initiator by using quantitative real-time in situ IR spectroscopy and monitoring the profiles of peaks in the range 1900-850 cm$\^$-1/. The conversion of acrylamide was calculated from the disappearance of the peak at 988 cm$\^$-1/, which is the out-of-plane bending mode of the=C-H unit, normalized to the C=O stretching peak at 1675 cm$\^$-1/, as an internal standard. For reaction temperatures in the range 40-65$^{\circ}C$ and initiator and monomer concentrations of 0.9-2.6 mmol/L and 0.5-1.1 mol/L, respectively, we deduced that the rate of monomer consumption follows the relation R$\_$p/=k[K$_2$S$_2$O$\_$8/]$\^$0.5/ [Μ]$\^$1.35${\pm}$0.10/. In addition, we obtained activation parameters from an evaluation of the kinetic data.

Cure Kinetics of Self-Extinguishing Epoxy Resin Systems with Charge Transfer Complex Type Latent Catalyst for Semiconductor Encapsulation (전하전이착체형 잠재성 촉매를 사용한 반도체 성형용 자소성 에폭시 수지 시스템의 경화 반응속도 연구)

  • Kim, Whan Gun
    • Journal of the Semiconductor & Display Technology
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    • v.13 no.4
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    • pp.27-32
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    • 2014
  • The cure properties of self-extinguishing epoxy resin systems with different charge transfer type latent catalysts were investigated, which are composed of YX4000H as a biphenyl epoxy resin, MEH-7800SS as a hardener, and charge transfer type latent catalysts. We designed and used five kinds of charge transfer type latent catalyst and compared to epoxy resin systems with Triphenylphosphine-Benzoquinone(TPP-BQ) as reference system. The cure kinetics of these systems were analyzed by differential scanning calorimetry with an isothermal approach, the kinetic parameters of all systems were reported in generalized kinetic equations with diffusion effects. The epoxy resin systems with Triphenylphosphine-Quinhydrone(TPP-QH), Triphenylphosphine-Benzanthrone(TPP-BT) and Triphenylphosphine-Anthrone(TPP-AT) as a charge transfer type latent catalyst showed a cure conversion rate of equal or higher rate than those with TPP-BQ. These systems with TPP-QH and Triphenylphosphine-Tetracyanoethylene(TPP-TCE) showed a critical cure reaction conversion of equal or higher conversion than those with TPP-BQ. The increases of cure conversion rates could be explained by the decrease of the activation energy of these epoxy resin systems. It can be considered that the increases of critical cure reaction conversion would be dependent on the crystallinity of the biphenyl epoxy resin systems.

Kinetic Studies of Alkaline Protease from Bacillus licheniformis NCIM-2042

  • Bhunia, Biswanath;Basak, Bikram;Bhattacharya, Pinaki;Dey, Apurba
    • Journal of Microbiology and Biotechnology
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    • v.22 no.12
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    • pp.1758-1766
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    • 2012
  • An extensive investigation was carried out to describe the kinetics of cell growth, substrate consumption, and product formation in the batch fermentation using starch as substrate. Evaluation of intrinsic kinetic parameters was carried out using a best-fit unstructured model. A nonlinear regression technique was applied for computational purpose. The Andrew's model showed a comparatively better $R^2$ value among all tested models. The values of specific growth rate (${\mu}_{max}$), saturation constant ($K_S$), inhibition constant ($K_I$), and $Y_{X/S}$ were found to be 0.109 $h^{-1}$, 11.1 g/l, 0.012 g/l, and 1.003, respectively. The Leudeking-Piret model was used to study the product formation kinetics and the process was found to be growth-associated. The growth-associated constant (${\alpha}$) for protease production was sensitive to substrate concentration. Its value was fairly constant up to a substrate concentration of 30.8 g/l, and then decreased.

Determination of reaction kinetics during vitrification of radioactive liquid waste for different types of base glass

  • Suneel, G.;Rajasekaran, S.;Selvakumar, J.;Kaushik, Chetan P.;Gayen, J.K.;Ravi, K.V.
    • Nuclear Engineering and Technology
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    • v.51 no.3
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    • pp.746-754
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    • 2019
  • Vitrification of radioactive liquid waste (RLW) provides a feasible solution for isolating radionuclides from the biosphere for an extended period. In vitrification, base glass and radioactive waste are added simultaneously into the melter. Determination of heat and mass transfer rates is necessary for rational design and sizing of melter. For obtaining an assured product quality, knowledge of reaction kinetics associated with the thermal decomposition of waste constituents is essential. In this study Thermogravimetry (TG) - Differential Thermogravimetry (DTG) of eight kinds of nitrates and two oxides, which are major components of RLW, is investigated in the temperature range of 298-1273 K in the presence of base glasses of five component (5C) and seven component (7C). Studies on thermal behavior of constituents in RLW were carried out at heating rates ranging from 10 to $40\;K\;min^{-1}$ using TG - DTG. Thermal behavior and related kinetic parameters of waste constituents, in the presence of 5C and 7C base glass compositions were also investigated. The activation energy, pre-exponential factor and order of the reaction for the thermal decomposition of 24% waste oxide loaded glasses were estimated using Kissinger method.

Control of a pressurized light-water nuclear reactor two-point kinetics model with the performance index-oriented PSO

  • Mousakazemi, Seyed Mohammad Hossein
    • Nuclear Engineering and Technology
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    • v.53 no.8
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    • pp.2556-2563
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    • 2021
  • Metaheuristic algorithms can work well in solving or optimizing problems, especially those that require approximation or do not have a good analytical solution. Particle swarm optimization (PSO) is one of these algorithms. The response quality of these algorithms depends on the objective function and its regulated parameters. The nonlinear nature of the pressurized light-water nuclear reactor (PWR) dynamics is a significant target for PSO. The two-point kinetics model of this type of reactor is used because of fission products properties. The proportional-integral-derivative (PID) controller is intended to control the power level of the PWR at a short-time transient. The absolute error (IAE), integral of square error (ISE), integral of time-absolute error (ITAE), and integral of time-square error (ITSE) objective functions have been used as performance indexes to tune the PID gains with PSO. The optimization results with each of them are evaluated with the number of function evaluations (NFE). All performance indexes achieve good results with differences in the rate of over/under-shoot or convergence rate of the cost function, in the desired time domain.

A Systems Engineering Approach to Multi-Physics Analysis of CEA Ejection Accident

  • Sebastian Grzegorz Dzien;Aya Diab
    • Journal of the Korean Society of Systems Engineering
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    • v.19 no.2
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    • pp.46-58
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    • 2023
  • Deterministic safety analysis is a crucial part of safety assessment, particularly when it comes to demonstrating the safety of nuclear power plant designs. The traditional approach to deterministic safety analysis models is to model the nuclear core using point kinetics. However, this simplified approach does not fully reflect the real core behavior with proper moderator and fuel reactivity feedbacks during the transient. The use of Multi-Physics approach allows more precise simulation reflecting the inherent three-dimensionality (3D) of the problem by representing the detailed 3D core, with instantaneous updates of feedback mechanisms due to changes of important reactivity parameters like fuel temperature coefficient (FTC) and moderator temperature coefficient (MTC). This paper addresses a CEA ejection accident at hot full power (HFP), in which the underlying strong and un-symmetric feedback between thermal-hydraulics and reactor kinetics exist. For this purpose, a multi-physics analysis tool has been selected with the nodal kinetics code, 3DKIN, implicitly coupled to the thermal-hydraulic code, RELAP5, for real-time communication and data exchange. This coupled approach enables high fidelity three-dimensional simulation and is therefore especially relevant to reactivity initiated accident (RIA) scenarios and power distribution anomalies with strong feedback mechanisms and/or un-symmetrical characteristics as in the CEA ejection accident. The Systems Engineering approach is employed to provide guidance in developing the work in a systematic and efficient fashion.

Symbolic-numeric Estimation of Parameters in Biochemical Models by Quantifier Elimination

  • Orii, Shigeo;Anai, Hirokazu;Horimoto, Katsuhisa
    • Proceedings of the Korean Society for Bioinformatics Conference
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    • 2005.09a
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    • pp.272-277
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    • 2005
  • We introduce a new approach to optimize the parameters in biological kinetic models by quantifier elimination (QE), in combination with numerical simulation methods. The optimization method was applied to a model for the inhibition kinetics of HIV proteinase with ten parameters and nine variables, and attained the goodness of fit to 300 points of observed data with the same magnitude as that obtained by the previous optimization methods, remarkably by using only one or two points of data. Furthermore, the utilization of QE demonstrated the feasibility of the present method for elucidating the behavior of the parameters in the analyzed model. The present symbolic-numeric method is therefore a powerful approach to reveal the fundamental mechanisms of kinetic models, in addition to being a computational engine.

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Kinetics and Mechanism of the Aminolyses of Bis(2-oxo-3-oxazolidinyl) Phosphinic Chloride in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.34 no.11
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    • pp.3218-3222
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    • 2013
  • The aminolyses, anilinolysis and pyridinolysis, of bis(2-oxo-3-oxazolidinyl) phosphinic chloride (1) have been kinetically investigated in acetonitrile at 55.0 and $35.0^{\circ}C$, respectively. For the reactions of 1 with substituted anilines and deuterated anilines, a concerted SN2 mechanism is proposed based on the selectivity parameters and activation parameters. The deuterium kinetic isotope effects ($k_H/k_D$) invariably increase from secondary inverse to primary normal as the aniline becomes more basic, rationalized by the transition state variation from a backside to a frontside attack. For the pyridinolysis of 1, the authors propose a stepwise mechanism with a rate-limiting step change from bond breaking for more basic pyridines to bond formation for less basic pyridines based on the selectivity parameters and activation parameters. Biphasic concave upward free energy relationship with X is ascribed to a change in the attacking direction of the nucleophile from a frontside attack with more basic pyridines to a backside attack with less basic pyridines.

Study of the Kinetics and Mechanisms of Alkoxy Radical Reactions in the Gas Phase (I). Arrhenius Parameters for t-Butoxy Radical Reactions with Isobutane and Cyclohexane

  • Song, Se-Ahn;Choo, Kwang-Yul
    • Bulletin of the Korean Chemical Society
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    • v.5 no.1
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    • pp.16-21
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    • 1984
  • The relative Arrhenius parameters for t-butoxy radical decomposition (log $A_d$, $E_d$) and hydrogen abstraction of t-butoxy radical from hydrogen donor (log $A_d$, $E_d$) by competitive method were obtained as follows: for cyclohexane; log $A_a/A_d$ = -4.17 mole/l and $E_d-E_a$ = 9.01 kcal/mole, for isobutane; log $A_a/A_d$ = -5.70 mole/l and $E_e-E_a$= 11.0 kcal/mole. From the reported Arrhenius parameters for t-Butoxy radical decomposition reactions the parameters for t-Butoxy radical reactions with isobutane and cyclohexane are estimated to be log $A(l/mol{\cdot}sec)$ = 8.4, $E_a$ = 4.3 kcal/mol and $log A (l/mol{\cdot}sec)= 9.9,\;E_a$ = 6.3 kcal/mol, respectively.