轮胎硫化程度的计算分析

根据对175／70R13型半钢子午线轮胎硫化过程数学模拟的温度场信息,利用Arrhenius方程计算轮胎各部位胶料的硫化程度,提出了评价胶料硫化程度的方法。结果表明,当硫化时间由原来的738s缩短为480s时,轮胎大部分部位的胶科由过硫状态转变为最佳硫化状态。     

Blends of bisphenol A‐based cyanate ester and bismaleimide: Cure and thermal characteristics

A dicyanate ester, namely, 2,2‐bis‐(4‐cyanatophenyl)propane, and a bismaleimide, namely, 2,2‐bis[4‐(4‐maleimido phenoxy)phenyl]propane, possessing closely resembling backbone structures, were cured together to derive bismaleimide–triazine network polymers of varying compositions. The blend manifested a eutectic melting behavior at a 1 : 1 composition with a eutectic melting point of 15°C. The cure characterization of the blends was done by DSC and dynamic mechanical analyses (DMA). The near simultaneous cure of the blend could be transformed to a clear sequential one by catalyzing the dicyanate cure to lower temperature using dibutyl tin dilaurate. The two‐stage, independent cure of the components of the blend evidenced in DSC was confirmed by DMA. The cure profile of the bismaleimide component predicted from the kinetic data derived from nonisothermal DSC was found to be in league with the isothermal DMA behavior. Both techniques led to optimization of the cure schedule of the blends. The cured polymers were characterized by FTIR and TGA. The cured blends underwent decomposition in two stages, each corresponding to the polycyanurate and polybismaleimide. Enhancing the bismaleimide component did not alter the initial decomposition temperature, but led to reduced rate of thermal degradation at higher temperature. Interlinking of the two networks and enhancing crosslink density through coreaction of the blend with 4‐cyantophenylmaleimide unaffected the initial decomposition properties but was conducive for increasing the char residue significantly. Computation of activation parameters for the thermal decomposition of the polymers confirmed that the first step in the degradation of the blends is caused by the polycyanurate component. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3365–3375, 1999     

Kinetic study of phenolic resin cure by IR spectroscopy

The cure reaction of a commercial phenolic resin (FRD‐5002, Borden Chimie S.A.) has been studied by IR spectroscopy (Fourier transform IR). A phenomenological approach was used to characterize the kinetic of reaction. Various kinetic models, including homogeneous reactions, diffusion‐controlled reactions, phase boundary movement, and nucleation and growth‐type kinetic, have been tested. Kinetic analyses using integral procedures on isothermal data indicate that the cure reaction data can be described above 140°C using the homogeneous first‐order reaction model. The activation energy has been found to be about 49.6 kJ mol⁻¹. At lower temperature, a diffusive mechanism was active, and the kinetic of reaction was well described by the Jander kinetic model. Because of the simple kinetic control active above 140°C, a mechanistic model for the resol cure at these temperatures has been also proposed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2703–2715, 1999     

Cure reaction of multi‐walled carbon nanotubes/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites: effect of carboxylic functionalization of MWCNTs

BACKGROUND: The aim of this work was to study, using differential scanning calorimetry, the effect of carboxylic functionalization of multi‐walled carbon nanotubes (MWCNTs) on the cure reaction of MWCNTs/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites. This is important for the practical design, analysis and optimization of novel materials processing. RESULTS: Comparing the influence of non‐functionalized MWCNTs and carboxyl‐functionalized MWCNTs, it was found that, at the initial curing stage, both MWCNTs act as catalyst and COOH functionalization of MWCNTs has a catalytic effect on the curing process. Then, at the later curing stage, non‐functionalized MWCNTs prevent the occurrence of vitrification, whereas COOH functionalization of MWCNTs promotes vitrification. Non‐functionalized MWCNTs decrease the degree of curing, as evidenced by lower total heat of reaction and lower glass transition temperatures of nanocomposites compared to neat epoxy; however, COOH functionalization of MWCNTs increases the degree of curing. CONCLUSION: For the development of composites, COOH functionalization of MWCNTs could bring a positive influence to the composite process. Its acceleration of cure could help shorten pre‐cure time or lower pre‐treatment temperature, and its effect of promoting vitrification could help shorten post‐cure time or lower post‐treatment temperature. Copyright © 2009 Society of Chemical Industry     

Cure kinetics modeling and process optimization of the vialux 81 epoxy photodielectric dry film (PDDF) material for microvia applications

The cure kinetics of a photodielectric dry film (PDDF) material called ViaLux 81 has been studied, with the aim of understanding and optimizing its curing schedule for the fabrication of sequentially built‐up (SBU) high‐density‐interconnect printed wiring boards (HDI‐PWB). Initial dynamic differential scanning calorimetry (DSC) scans on the material revealed a two‐stage curing mechanism due to the long lifetime of the photoinitiator catalyst, which could not be separated at lower heating rates. On the other hand, the heat flow exotherm from isothermal DSC experiments showed a rapid reaction rate at the beginning with only a single peak. Therefore, to capture the complexity of the process, the faster multiple heating rate DSC experiments are used to predict the degree‐of‐cure (DOC) evolution. Two approaches have been developed based on the dynamic DSC data: (1) a “model‐free” approach, which only requires information about the cure‐dependence of the activation energy; and (2) a practical scheme to deconvolute the two curing peaks. Excellent agreement is observed for the heating rate experiments, but the methods are inadequate for predicting the DOC evolution under isothermal conditions. Therefore, a modified autocatalytic model with temperature‐dependent kinetic parameters has been developed based on the isothermal DSC data. This model predicts the DOC evolution for isothermal curing profiles very well. However, some discrepancy is evident in predicting the DOC evolution for heating rate experiments, due to the underestimation of the activation energy. With appropriate corrections, excellent predictive capability is illustrated for complex cure schedules with combined heating rate and isothermal segments. In addition, a cure process optimization strategy has been suggested, and the fabrication of fine features and microvias is demonstrated. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 691–700, 2002; DOI 10.1002/app.2345     

Thermal analysis of curing process of epoxy prepreg

The curing process of epoxy prepreg was studied by means of differential scanning calorimetry analysis. The dynamic, isothermal, and combinations of dynamic and isothermal measurements were done over selected temperature ranges and isothermal cure temperatures. The heats of reaction for dynamic and isothermal cure were determined. The results show that the heat of the isothermal‐cure reaction increased with the increment of temperature. The degree of cure was calculated from the heat of the isothermal‐cure reaction. The complete cure reaction could be achieved at 220°C within a very short cure time. The changes of cure rate with time were given for the studied isothermal cure temperatures. To simulate the relationship between the cure rate and degree of cure, the autocatalytic model was used and the four parameters were calculated. Except in the late stage of the cure reaction, the model agrees well with the experimental data, especially at high temperatures. To account for the effect of diffusion on the cure rate, a diffusion factor was introduced into the model. The modified model greatly improved the predicted data at the late stage of cure reaction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1074–1083, 2002     

L4．00R20越野子午线轮胎的硫化测温

介绍14．00R20越野子午线轮胎的硫化测温过程,绘制测温曲线,利用胶料的活化能和测温数据计算各部位胶料的硫化程度。结果表明：轮胎硫化条件和各部位硫化程度较理想,胎侧中部的硫化程度最大,达到400％以上;胎冠肩部的硫化程度最小,不到100％。     

Optimal curing for thermoset matrix composites: Thermochemical considerations

A design sensitivity analysis is used to optimize the applied wall temperature vs. time in autoclave curing for thermoset matrix composites. The calculation minimizes the cure time and obeys a maximum temperature constraint in the composite. The transient, coupled thermal and cure problem is solved by a finite element method. Design sensitivity information is extracted efficiently from this primal analysis, based on an analytical, direct differentiation approach. The sensitivities are then used with gradient‐based optimization techniques to systematically improve the curing process. The optimal cure cycles for different numbers of temperature dwells may be similar (for a 2 mm thick part) or very different (for a 4 cm thick part), depending on the nature of the problem. In the latter case a large reduction of cure time is obtained when a three‐dwell cure cycle is used, and the optimizer has more flexibility to adjust the cure cycle. This systematic optimization approach provides a powerful and practical means of optimizing composite manufacturing processes.     

Cure reaction for modified diallylbisphenol A/diaminodiphenylsulfone/bismaleimide

The glass‐transition temperature as a function of curing conversion for a modified diallylbisphenol A/diaminodiphenylsulfone/bismaleimide (BMI) resin was investigated at different temperature regimes and modeled using a modified Di Benedetto equation. Although the relationship between the glass‐transition temperature and conversion of the BMI system conforms to the Di Benedetto equation for α < 0.6 and at lower cure temperatures, at higher cure temperatures the results deviated significantly from the equation; thus, it was an inadequate model for the system. Fourier transform IR analysis showed that the major crosslinking reactions did not occur during cure for the modified BMI at and below 150°C. However, as the cure temperature was increased, the crosslinking reactions responsible for 3‐dimensional network structures became more dominant. At 190°C the C? N? C_stretch vibration of the uncured maleimide ring converted into succinimide rings in the curing process. Simultaneously, a decrease was observed for the absorbance bands of ? C? H_bending (maleimide). The higher cure temperatures induced a significantly faster initial crosslinking rate and also resulted in a shorter period of time after which further crosslinking was retarded, because the increase in the crosslinks also physically slowed further crosslinking activity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 227–235, 2002     

Optimal design of a multi-product biorefinery system

In this paper we propose a biorefinery optimization model that can be used to find the optimal processing route for the production of ethanol, butanol, succinic acid and blends of these chemicals with fossil fuel based gasoline. The approach unites transshipment models with a superstructure, resulting in a Mixed Integer Non-Linear Program (MINLP). We consider a specific problem based on a network of 72 processing steps (including different pretreatment steps, hydrolysis, fermentation, different separations and fuel blending steps) that can be used to process two different types of feedstock. Numerical results are presented for four different optimization objectives (maximize yield, minimize costs, minimize waste and minimum fixed cost), while evaluating different cases (single product and multi-product).     

Dependence of Mooney scorch time of SMR L,ENR 25, and ENR 50 on concentration and types of antioxidants

The effect of concentration of antioxidants on the Mooney scorch time of two grades of epoxidized natural rubbers (ENR 25 and ENR 50) and one grade of natural rubber (SMR L) was studied using a Monsanto automatic Mooney viscometer (MV 2000). Three types of antioxidants, viz., 2,2′‐methylene‐bis(4‐methyl, 6‐tertbutylphenol) (AO 2246), N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine (IPPD) and poly‐2,2,4‐trimethyl‐1,2‐dihydroquinoline (TMQ) were used, and the concentration range was varied from 0 to 5 phr. The conventional vulcanization system with 2‐mercaptobenzothiazole (MBT) as the accelerator was used throughout the study. Results show that increasing the phenol‐based antioxidant (AO 2246) concentration will increase the scorch time of ENR at a lower temperature of vulcanization while its effect on SMR L is not significant. This retardation effect is attributed to the “solvation” of epoxide group by the phenolic group in AO 2246, thus reducing the activation of adjacent double bond in ENR. The scorch time, however, is shortened by the amine‐based antioxidants (IPPD and TMQ) for the three rubbers studied, a phenomenon associated with the ability of the amine group to enhance the formation of more active sulfurating agent and subsequently increases the cure rate as the concentration of the amine‐based antioxidants is increased. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2940–2946, 1999     

Studies on rubber‐to‐nylon tire cord bonding

Nylon tire cord (1680/2) was dipped in different adhesives based on resorcinol formaldehyde resin and latex (RFL) and was bonded to natural rubber‐based compounds. The resin‐rubber ratio in the RFL adhesive was optimized. The variation of pull‐through load was studied by varying the drying and curing temperature of the dipped nylon tire cord. RFL adhesive based on vinylpyridine latex was found to have better rubber‐to‐nylon tire cord bonding, compared with the one based on natural rubber latex. Addition of a formaldehyde donor into the RFL adhesive/rubber compound improves adhesion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1197–1202, 1999     

Mathematical modeling and experimental study of conveyor belt continuous curing process

A mathematical model was developed to predict the temperature distribution within various layers of conveyor belts during the continuous curing process. The results predicted by the model are found to be in good agreement with the experimental results, hence justifying the capability of the model for simulation of the conveyor belt continuous process. This information was utilized to provide more insight into the curing process in terms of the state of cure (SOC) and/or the degree of conversion, which may, in turn, be utilized for the optimization of the curing process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2448–2454, 2000     

Cure properties of epoxies with varying chain length as studied by DSC

The cure of diglycidyl ether of bisphenol A (DGEBA) and a homologous series of poly(ethylene oxide) diglycidyl ether (PEODE) epoxy resins with 4,4′‐diaminodiphenyl sulfone (DDS) was studied by scanning and isothermal differential scanning calorimetry (DSC). The heat of polymerization was relatively independent of monomer structure and chain length when determined by isothermal DSC. Variations in the heats of polymerization determined by the scanning method were attributed to degradative reactions at higher temperatures during the scan. The activation energies determined by scanning DSC experiments were relatively constant at 61 ± 3 kJ/mol. However, using an isothermal cure method, the activation energies were found to vary with monomer structure and extent of cure. The isothermal kinetics were analyzed in terms of the autocatalytic model on the basis of competing reaction paths involving catalysis by either initial impurities or hydroxyl groups produced in situ. The activation energies of both reaction paths were found to vary with monomer structure and degree of conversion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1479–1488, 1999     

Numerical simulation of localized cure of thermosensitive resin during thermo stereolithography process (TSTL)

In this work, to analyze a type of rapid prototyping technique, a numerical model was developed that was able to simulate the heat transfer at thermosensitive polymeric material during cure by laser irradiation. The analysis was carried out as a transient thermal problem using the general‐purpose finite element software ANSYS. The technique analyzed was thermal stereolithography, which uses a CO₂ laser beam to cure (solidify) thermosensitive liquid resins in a selective way to produce three‐dimensional parts. In this numerical analysis, the temperature distribution at thermoset material heated by a laser irradiation and its thermal properties are investigated. This resin is a high‐viscosity sample composed of epoxy resin, diethylenetriamine, and silica powder, which become highly crosslinked when irradiated by infrared laser. The localized curing becomes critical when the amount of silica and laser parameters are not appropriate. Bearing this in mind, this work intends, by applying the numerical method developed, to analyze the thermal behavior of resins in function of amount of silica and the laser radiation conditions, so that it is possible to have a knowledge on these variables so as to achieve a product with the required specifications. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2777–2783, 2006     

Cure kinetics of T700/BMI prepreg used for advanced thermoset composite

A new isothermally based, cure kinetic model for the prepreg was presented using an industrially supplied prepreg rather than pure resin. The matrix resin was bismaleimide (BMI) resins, and the reinforcement was carbon fiber T700–12S. The BMI prepreg was measured from 170 to 220°C by isothermal DSC. The isothermal cure reaction heat increases with the increment of cure temperature. The DSC data were analyzed by the proposed nth‐order reaction model. An increase in reaction rate was observed at higher temperature in both neat and prepreg. After reaching the peak value, the reaction rate dropped off faster in prepreg, resulting in a lower average value of the ultimate heat of reaction. It was suggested the presence of carbon fiber had an effect on the cure kinetics as a heat sink. The carbon fibers imposed restrictions on the molecular mobility of the reactive species and did not change the cure mechanism. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2238–2241, 2005     

Low‐temperature photopolymerization and post‐cure characteristics of acrylates

Near‐infrared spectroscopy was used to investigate the post‐cure characteristics of acrylates polymerized from ? 75 °C up to room temperature. The results obtained showed that the double bond conversion increased with increasing initiator concentration. Post‐cure was much more striking for samples cured at lower temperatures. The chemical structure of monomer and photoinitiator had a great effect on the post‐cure process. The greater the functionality, the lower the final double bond conversion and the more distinct the post‐cure effect. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry     

Modeling the evolution of the dynamic mechanical properties of a commercial epoxy during cure after gelation

The cure kinetics for a commercial epoxy have been established and the influence of the degree of cure on the glass transition determined. Time‐temperature and time‐conversion superposition principles have been built into a model that successfully predicts the development of the viscoelastic properties of the epoxy during isothermal cure from gelation to after vitrification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 495–508, 2000     

Phenolic resins with phenyl maleimide functions: Thermal characteristics and laminate composite properties

Phenolic resins bearing varying concentrations of phenyl maleimide functions were synthesized by copolymerizing phenol with N‐(4‐hydroxyphenyl)maleimide (HPM) and formaldehyde in the presence of an acid catalyst. The resins underwent a two‐stage curing, through condensation of methylol groups and addition polymerization of maleimide groups. The cure characterization of the resin by dynamic mechanical analysis confirmed the two‐stage cure and the dominance of maleimide polymerization over methylol condensation in the network buildup process. The kinetics of both cure reactions, studied by the Rogers method, substantiated the earlier proposed cure mechanism for each stage. Although the initial decomposition temperature of the cured resin was not significantly improved, enhancing the crosslink density through HPM improved thermal stability of the material in a higher temperature regime. The anaerobic char yield also increased proportional to the maleimide content. Isothermal pyrolysis and analysis of the char confirmed that pyrolysis occurs by loss of hydrocarbon and nitrogenous products. The resins serve as effective matrices in silica‐ and glass fabric–reinforced composites whose mechanical properties are optimum for moderately crosslinked resins, in which failure occurs through a combination of fiber debonding and resin fracture. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1664–1674, 2001