Curing kinetics of arylamine-based polyfunctional benzoxazine resins by dynamic differential scanning calorimetry

In this study, the curing kinetics of polyfunctional benzoxazine resins based on arylamine, i.e. aniline and 3,5-xylidine, designated as BA-a and BA-35x, respectively, were investigated. Non-isothermal differential scanning calorimetry (DSC) at different heating rates is used to determine the kinetic parameters and the kinetic models of the curing processes of the arylamine-based polyfunctional benzoxazine resins were proposed. Kissinger, Ozawa, Friedman, and Flynn-Wall-Ozawa methods were utilized to determine the kinetic parameters of the curing reaction. BA-a resin shows only one dominant autocatalytic curing process with the average activation energy of 81-85 kJ mol⁻¹, whereas BA-35x exhibits two dominant curing processes signified by the clear split of the curing exotherms. The average activation energies of low-temperature curing (reaction (1)) and high-temperature curing (reaction (2)) were found to be 81-87 and 111-113 kJ mol⁻¹, respectively. The reaction (1) is found to be autocatalytic in nature, while the reaction (2) exhibits nth-order curing kinetics. In addition, the predicted curves from our kinetic models fit well with the non-isothermal DSC thermogram.     

Kinetic analysis of isothermal decomposition of 2,4-dinitrophenylhydrazine using differential scanning calorimetry

Differential scanning calorimetry was used to study the thermal decomposition of 2,4-dinitrophenylhydrazine (DNPH) in isothermal regime. The DSC curves were carried out at several constant temperatures lower than the melting temperature. The standard isoconversional analysis of the obtained curves suggests an autocatalytic decomposition mechanism. This mechanism is also supported by the temperature dependence of the observed induction periods.     

Investigation of the curing reactions of some multifunctional epoxy resins using differential scanning calorimetry

Curing reaction of three tetrafunctional epoxy resins in the presence of tetraethylene tetramine was examined by differential scanning calorimetry at different heating rates. The kinetic parameters of the curing reaction were determined using various computational methods (Barrett, Borchardt–Daniels and Kissinger). The heating rate shows a great influence on the curing process. The activation energy varied in the range 43–80 kJ/mol, and the order of the curing reaction is observed to be ≈1.0 with slight variations.     

基于松香酸酐的环氧树脂体系固化动力学及TTT图绘制

研制了基于松香酸酐固化剂的生物质环氧树脂体系,采用全动态DSC法研究了树脂体系的固化反应动力学,通过半经验的唯象模型拟合得到了固化反应参数,活化能Ea为59.68 kJ/g,指前因子A0为1.28×1015s-1,反应级数n为2.483,由此建立了体系固化温度/时间/固化度间的关系;采用恒温DSC及DMA方法测试玻璃化转变温度,应用DiBenedetto经验方程拟合得到了玻璃化转变温度与固化度间的关系.应用锥板旋转黏度计测试了树脂体系不同温度下的凝胶时间,通过线性回归分析得到了凝胶时间与温度之间的关系.由唯象模型和DiBenedetto方程分别计算得到凝胶时的固化度为0.386,玻璃化转变温度为26.22°C.由上述工作绘制了基于松香酸酐生物质树脂体系的TTT(time-temperature-transition diagram)固化图,可确定树脂体系在不同温度任意时间下的状态.     

Isothermal curing of an epoxy resin by alternating differential scanning calorimetry

The quasi-isothermal curing of a diepoxide resin with a triamine of polyoxypropylene was studied by alternating differential scanning calorimetry (ADSC), which is a temperature modulated DSC technique. The complex heat capacity measurements allows to analyse the vitrification process at curing temperatures (T_c) below the maximum glass transition of the fully cured epoxy (T_g∞=85.8°C). Initially, the modulus of the complex heat capacity, |C^*_p|, increases until a maximum (conversion between 0.42 and 0.56) and then decreases. This step is followed by an abrupt decay of |C^*_p|, due to the vitrification of the system, which allows the determination of the vitrification time. This value agrees well with that determined by the partial curing method. The phase angle and out-of-phase heat capacity show an asymmetric wide peak during the vitrification process. The change in |C^*_p| at vitrification decreases with the increase of T_c becoming zero at temperature T_g∞. This epoxy-triamine system shows a delay of the vitrification process respect to other model epoxy systems probably due to the presence of polyoxypropylene chains in the network.

The decay of |C^*_p| during vitrification may be normalised between unity and zero by defining a mobility factor. This mobility factor has been used to simulate the reaction rate during the stage where the reaction is controlled by diffusion. The observed reaction rate is simulated by the product of the kinetic reaction rate, determined by the autocatalytic model, and the mobility factor.     

Cure Kinetics of DGEBA with Hyperbranched Poly （3-hydroxyphenyl） Phosphate as Curing Agent Studied by Non-isothermal DSC

IntroductionEpoxy resins are widely used in the fields of coa-tings,adhesives,insulating materials,etc..Diglycidylether of bisphenol A(DGEBA)is the most importantepoxy resin in industry because of its fluidity,physicaland mechanical properties after cure,…     

Crystallization kinetics of poly(ethylene adipate) investigated by differential scanning calorimetry

Crystallization of poly(ethylene adipate) from the amorphous state under non-isothermal conditions with several heating rates has been investigated. The activation energy values, evaluated for different degrees of conversion, using the Ozawa plot, show a slightly decreasing tendency for the higher degrees of conversion.

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Zusammenfassung Es wurde die Kristallisation von Polyethylenadipat aus dem amorphen Zustand unter nichtisothermen Bedingungen und mit verschiedenen Aufheizgeschwindigkeiten untersucht. Die unter Anwendung der Darstellung von Ozawa für verschiedene Konversionsraten erhaltenen Werte für die Aktivierungsenergie zeigen für höhere Konversionsraten eine leicht sinkende Tendenz.

     

Critical thermodynamic analysis of differential scanning calorimetry for studying chemical kinetics

A critical thermodynamic analysis of differential thermal calorimetry is reported herein to gain further insight into the phenomena leading to the reported differences between kinetic parameters extracted from isothermal DSC methods and those from dynamic DSC methods. The sources have been identified for the variations observed in the total heat of reaction as a function of the heating rate in dynamic DSC experiments. The analysis clearly indicates that these variations are, in fact, to be anticipated. The relationships necessary for extracting kinetic data from both isothermal and dynamic experiments are derived rigorously by resorting to classical thermodynamics. This work was supported by the Cooperative State Research Service, U.S. Department of Agriculture, under Agreement No. 92-37500-7911.     

Photo-curing kinetics for the UV-initiated cationic polymerization of a cycloaliphatic diepoxide system photosensitized by thioxanthone

Photo-differential scanning calorimetry (photo-DSC) was used to investigate the cure kinetics for the UV-initiated cationic photo-polymerization of cycloaliphatic diepoxide (CADE) systems with and without a photo-sensitizer, 2,4-diethylthioxanthone (DETX), in the presence of a diaryliodonium-salt photo-initiator. Two kinetics parameters—the rate constant (k) and the order of the initiation reaction (m)—were determined for the CADE epoxide system for different amounts of added DETX photo-sensitizer (0-1 wt%) and at different isothermal temperatures (25-100 °C) using an autocatalytic kinetics model. The photo-sensitized CADE epoxide system gave much higher k and m values than the nonphoto-sensitized one (due to the photo-sensitization effect). Moreover, k and m for both CADE epoxide systems with and without DETX increased significantly with increasing isothermal temperature due to a thermal contribution towards increasing the mobility of active species. We also observed that the addition of DETX lowered the activation energy for the UV-curable epoxide system; the collision factor for the system with DETX was higher than that obtained for the system without DETX, indicating that the reactivity of the former was greater than that of the latter due to the photo-sensitization effect.     

Nonisothermal crystallization kinetics of in situ nylon 6/graphene composites by differential scanning calorimetry

The nonisothermal crystallization kinetics was investigated by differential scanning calorimetry for the nylon 6/graphene composites prepared by in situ polymerization. The Avrami theory modified by Jeziorny, Ozawa equation, and Mo equation was used to describe the nonisothermal crystallization kinetics. The analysis based on the Avrami theory modified by Jeziorny shows that, at lower cooling rates (at 5, 10, and 20 K/min), the nylon 6/graphene composites have lower crystallization rate than pure nylon 6. However, at higher cooling rates (at 40 K/min), the nylon 6/graphene composites have higher crystallization rate than pure nylon 6. The values of Avrami exponent m and the cooling crystallization function F(T) from Ozawa plots indicate that the mode of the nucleation and growth at initial stage of the nonisothermal crystallization may be as follows: two‐dimensional (2D), then one‐dimensional (1D) for all samples at 5–10 °C/min; three‐dimensional (3D) or complicated than 3D, then 2D and 1D at 10–20 and 20–40 °C/min. The good linearity of the Mo plots indicated that the combined approach could successfully describe the crystallization processes of the nylon 6 and nylon 6/graphene composites. The activation energies (ΔE) of the nylon 6/graphene composites, determined by Kissinger method, were lower than those of pure nylon 6. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1381–1388, 2011     

Cure kinetics of carbon nanotube/tetrafunctional epoxy nanocomposites by isothermal differential scanning calorimetry

The cure kinetics of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) and 4,4′‐diaminodiphenylsulfone (DDS) as a cure agent in nanocomposites with multiwalled carbon nanotubes (MWNTs) have been studied with an isothermal differential scanning calorimetry (DSC) technique. The experimental data for both the neat TGDDM/DDS system and for epoxy/MWNTs nanocomposites showed an autocatalytic behavior. Kinetic analysis was performed with the phenomenological model of Kamal and a diffusion control function was introduced to describe the cure reaction in the later stage. Activation energies and kinetic parameters were determined by fitting experimental data. For MWNTs/epoxy nanocomposites, the initial reaction rates increased and the time to the maximum rate decreased with increasing MWNTs contents because of the acceleration effect of MWNTs. The values of the activation energies for the epoxy/MWNTs nanocomposites were lower than the values for the neat epoxy in the initial stage of the reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3701–3712, 2004     

Nucleation and crystallization kinetics of polyamide 12 investigated by fast scanning calorimetry

Nucleation and crystallization of polyamide 12 (PA 12) have been systematically investigated by fast scanning calorimetry at non-isothermal and isothermal conditions. The critical cooling rates of crystallization and crystal nucleation were determined as 300 and 10,000 K/s, respectively. Moreover, the half-times of nucleation (t_1/2,nucl) and overall crystallization (t_1/2,cry) show monomodal and bimodal dependencies on the crystallization temperature. t_1/2,nucl has an approximate minimum value of about 0.0005 s at 333 K, which is about 10–20 K above the glass transition temperature, and t_1/2,cry has two minima of about 0.05 and 0.8 s at about 333 and 383 K, respectively. Comparing the crystallization behavior of PA 12 with other polyamides, the activation energy for crystallization increases and the energy barrier of short-range diffusion decreases with the increase of the amide-group density in the chains.     

Synthesis and Characterization of a Novel Curing Agent for Epoxy Resin Based on Phosphazene Derivatives

In this work, a novel amine-terminated curing agent for epoxy resin based on hexachlorocyclotriphosphazene (HCCP) was synthesized through two steps of nucleophilic substitution reactions by phenol and 4-aminophenol. Its chemical structure was characterized by ¹H-NMR, Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS). This curing agent was liquid at room temperature which made it easy to disperse in the epoxy resin. The rheological test showed the viscosity of the pre-polymer fluid decreased as the proportion of the curing agent increased so it improved the process performance. The curing reaction was studied by differential scanning calorimeter (DSC). The novel curing agent had a wider range of curing temperature and relatively lower curing temperature in comparison with the widely-using curing agent 4,4′-Diaminodiphenylmethane (DDM). The wider range of curing temperature helped lower the heat accumulation which was an important factor in curing process.     

酸酐固化环氧树脂/蒙脱土复合材料的等温固化动力学

用等温差示扫描量热法(DSC)研究了酸酐固化环氧树脂/蒙脱土复合材料的等温固化过程，考察了未处理的蒙脱土(MMT)和有机蒙脱土(OMMT)对环氧树脂固化动力学的影响. 实验表明， 环氧树脂的固化过程包含自催化机理，加入蒙脱土没有改变固化反应机理. 用Kamal方程对该体系的固化过程进行拟合，得到反应级数m、n，反应速率常数k1、k2，总反应级数(m + n)在2.4～3.0之间. MMT的加入使环氧树脂体系的k1、k2有所降低，而OMMT的加入对体系的k1、k2影响较为复杂，加入蒙脱土对环氧树脂固化体系的活化能影响较小.     

Polymerization kinetics of acrylic bone cements by differential scanning calorimetry

Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.     

A differential scanning calorimetry method to determine the isothermal crystallization kinetics of cocoa butter

This research aimed to reduce the variability on the data obtained from differential scanning calorimetric (DSC) analysis of the isothermal crystallization kinetics of cocoa butter.

To enable transformation of the DSC crystallization peak to a sigmoid crystallization curve, the DSC peak area has to be integrated. Usually, the start and end points of the crystallization peak are determined visually. The result of this visual determination appeared to be very much dependent on the operator, but also differed considerably when the same operator performed the integration several times. By proposing an objective calculation algorithm to determine the start and end points of integration, the variability caused by the operator during the integration procedure could be eliminated. Furthermore, sample preparation and the DSC heating protocol to melt the sample prior to crystallization were studied. Three heating protocols (65 °C for 15 min, 65 °C for 30 min and 80 °C for 15 min) were compared and it was shown that holding at 65 °C for 15 min was sufficient to eliminate any influence of sample history. Two different sample preparation procedures were compared and it appeared that a change in sample preparation procedure had a significant influence on the measured crystallization process. It is thus important to keep this method constant to eliminate the variability caused by it.     

Investigation on nonisothermal crystallization kinetics of the high‐flow nylon 6 by differential scanning calorimetry

The crystallization kinetics of the high‐flow nylon 6 containing polyamidoamine (PAMAM) dendrimers units in nylon 6 matrix was investigated by differential scanning calorimetry. The Ozawa and Mo equations were used to describe the crystallization kinetics under nonisothermal condition. The values of Avrami exponent m and the cooling crystallization function F(T) were determined from the Ozawa plots, which showed bad linearity, and were divided into three sections depending on different cooling rates. The plots of the m and log F(T) values versus crystallization temperatures were obtained, which indicated that the actual crystallization mechanisms might change with the crystallization temperatures. The high‐flow nylon 6 has higher values of m and log F(T) than those of pure nylon 6, which implied that the high‐flow nylon 6 had more complicated crystallization mechanisms and slower crystallization rate than those of pure nylon 6. The good linearity of the Mo plots verified the success of this combined approach. The activation energies of the high‐flow nylon 6 ranged from 157 to 174 kJ/mol, which were determined by the Kissinger method. The ΔE values were lower than those of pure nylon 6, and the ΔE values were affected by both the generation and the content of PAMAM units in the nylon 6 matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2201–2211, 2008     

FTIR法研究环氧树脂固化反应动力学

用傅里叶红外光谱（ＦＴＩＲ）法研究了双酚Ｓ环氧树脂和甲溴双酚Ａ环氧树脂分别与二胺基二苯砜在恒温条件下的固化反应动力学,得出了各反应的表观活化能。     

Kinetic study of polyurethanes formation by using differential scanning calorimetry

Kinetics of polyurethane formation between several polyols and isocyanates with dibutyltin dilaurate (DBTDL) as the curing catalyst, were studied in the bulk state by differential scanning calorimetry (DSC) using an improved method of interpretation. The molar enthalpy of urethane formation from secondary hydroxyl groups and aliphatic isocyanates is 72±3 kJ mol^-1 and for aromatic isocyanates it is 55±2 kJ mol^-1 . In the case of a single second order reaction for aliphatic isocyanates reaction, activation energy is 70±5 kJ mol^-1 with oxypropylated polyols and 50±3 kJ mol^-1 with Castor oil. For aromatic isocyanates and oxypropylated polyols the activation energy is higher around 77 kJ mol^-1 . In the case of two parallel reactions (situation for IPDI and TDI 2-4) best fits are observed considering two different activation energies.