Techniques used for determining cure kinetics of rubber compounds

Controlling and assuring the quality of the manufacture of high precision engineering rubber components has led to the need to simulate fundamental industrial processes such as compression molding and injection molding using CAE tools. Both compression and injection molding techniques for the fabrication of rubber products involve crosslinking or vulcanization which is invariably assisted by temperature and pressure. Vulcanization is a chemical process and therefore its simulation necessarily involves characterization of kinetic parameters. The kinetics of curing or vulcanization is somewhat complex as it depends upon the compound formulation, temperature and in some cases pressure. The present paper reports and discusses the application and utility of different techniques for characterizing the cure behavior of rubber compounds. Kinetic data has been fitted to various mathematical models in order to see which of the models can best represent the crosslinking behavior of selected rubber compounds. Finally, the kinetic data is used to simulate the injection molding process for relatively simple geometries.     

Monitoring the vulcanization of elastomers: Comparison of curemeter and ultrasonic online control

The vulcanization of elastomeric materials has a high impact on the properties of the final product. Therefore, it is important to monitor and control this crosslinking process. A common technique to attain the necessary curing time is the use of a curemeter in accordance with ISO 6502 in order to determine the time for full cure of a sample with a standardized geometry. Based on this result and a lot of practical experience, the required curing time for a given product geometry is estimated. Within the scope of this work, a new analysis technique will be compared with the standard procedure. The ultrasonic online control employs ultrasound waves to measure the changes in material properties caused by vulcanization. For this study, a natural rubber compound with a conventional curing system was investigated by both techniques. It was found that the results of the ultrasonic technique show good agreement with the results of the curemeter.     

The effect of mercapto- and thioacetate-modified EPDM on the curing parameters and mechanical properties of natural rubber/EPDM blends

The vulcanization characteristics of natural rubber (NR)/ethylene-propylene-ethylidenenorbornene (EPDM) rubber blends were studied in the presence of thioacetate-(EPDMTA) or mercapto-modified EPDM (EPDMSH), using oscillating disk rheometer. The effect of both functionalized EPDMs was investigated in unaccelerated-sulfur curing system and accelerated-sulfur curing systems containing 0.4 and 0.8 phr of MBTS. Both EPDMTA and EPDMSH act as accelerator agent in the curing process, as indicated by the higher values of cure rate index and lower values of activation energy of vulcanization. A substantial increase of the crosslink density has been also observed in EPDMSH-modified blends. Both EPDMTA and EPDMSH resulted in an increase in tensile strength, but the best performance has been achieved with EPDMSH, probably because of the increase of crosslink density associated to the reactive compatibilization promoted by the reaction between mercapto groups and rubber matrix. The best ageing resistance has been observed in EPDMTA-modified blends.     

金属-橡胶硫化粘接研究进展

综述金属 -橡胶胶粘剂及粘接技术进展 ,回顾其发展过程 ,分析不同粘接体系的优缺点 ;探讨金属-橡胶粘接过程中的某些问题及影响粘接的多种因素 ,并对下一步的研究发展提出了部分建议。     

Matching Cure Characteristics of Automotive Rubber Compound and Polyurethane Coating

The present investigation focuses on matching cure characteristics of EPDM rubber compound and polyurethane (PU) coating using temperature modulated and pressure differential scanning calorimetry (TMDSC, PDSC). TMDSC provides a detailed and better understanding of the curing process of model rubber system as well as complex automotive rubber compounds. The low level of unsaturation present in EPDM, results in the small heat of vulcanization (2–5 J g^–1), which is difficult to accurately measure using conventional differential scanning calorimetry (DSC). Thus, curing of highly filled EPDM compound was investigated using TMDSC. The kinetics of PU curing was monitored using pressure DSC (PDSC), and heat of curing was determined as 4.2 J g^–1 at 10°C min^–1 heating rate. It is found that complex automotive compounds and the PU coating are curing simultaneously. This revised version was published online in July 2006 with corrections to the Cover Date.     

A new simple numerical model based on experimental scorch curve data fitting for the interpretation of sulphur vulcanization

Sulphur was the first agent used to vulcanize commercial elastomers (e.g. natural rubber) and allows meaningful cost reductions during the industrial process (production cost ratio between peroxides and accelerated sulphur is around 5). Therefore, accelerated sulphur vulcanization is the most popular technique for the production of polydiene and EPDM elastomers items. At present, crosslinking mechanisms are not analytically known in detail, therefore reticulation kinetic has to be deduced from mechanical properties obtained during standardized tests, as for instance the oscillating disc rheometer. In the present paper, we propose a numerical model to fit experimental rheometer data based on a simple composite three functions curve, able to describe the increase of the viscosity at successive curing times at different controlled temperature to use during the production of thick items vulcanized with sulphur. It is believed that rheometer curve is able to give an indirect information on the rubber reticulation kinetic at different temperatures, to use in a successive step to establish simplified analytical kinetic formulas to adopt in the accelerated sulphur vulcanization of polydiene and EPDM elastomers. In the model, it is necessary to collect rheometer curves at different specimen temperatures, because vulcanization in industrial practice occurs at variable temperatures during curing, with considerable differences from the core to boundary of the item. Once that rheometer curves are suitably collected in a database, they are used to predict the optimal vulcanization of real items industrially produced. Finally, a so called alternating tangent approach (AT) is implemented to determine optimal input parameters (curing external temperature T _n and rubber exposition time t) to use in the production process. Output mechanical property (objective function) to optimize is represented by the average tensile strength of the item. A meaningful example of engineering interest, consisting of a thick 2D EPDM cylinder is illustrated to validate the model proposed.     

Studies of conventional sulfur vulcanization of SBR rubber: Analysing the reaction products from thermal degradation of the accelerator by means of MCC-IMS technique

A combination of knowledge on curing process of rubber mixes with novel methods of chemical analysis, a new unconventional approach to analysis of rubber vulcanization is presented in this study. Six SBR samples containing various N-tert-butyl-2-benzothiazole sulfenamide (TBBS) accelerator: sulfur ratios (within) the range of conventional (CV) sulfur vulcanization system were studied using multi-capillary column ion mobility spectrometry (MCC-IMS) technique. For these analysis, calibration/dilution curves were established. Moreover, data from MCC-IMS were correlated with other parameters of the rubber vulcanizates – their crosslink density and structure as well as their tensile strength and modulus at elongation. For such comparison, one of the reaction products from thermal decomposition of TBBS, benzothiazole was selected. Furthermore, the concentration of benzothiazole released during the vulcanization process corresponded well with the crosslink density of the rubber vulcanizates studied. It was even possible to calculate the crosslink density from the concentration of benzothiazole determined by MCC-IMS, using Boltzmann fitting curve. The presented results could be an important contribution in understanding the mechanisms occurring during rubber vulcanization, demonstrating a new approach to testing and evaluation of the process.     

Mechanistic modeling of reversion phenomenon in sulphur cured natural rubber vulcanization kinetics

A novel kinetic model of natural rubber sulphur vulcanization is proposed. The modeling approach takes into account current knowledge on the different polysulfidic structures present during vulcanization, and the associated individual reactions. A simplified scheme is proposed, giving a mechanistic view of the reversion phenomenon, which results in a decrease of the elastic modulus (related to the sulphur crosslink density) for long vulcanization times at high temperature. The resulting set of differential equations is solved by an appropriate numerical method to predict the evolution of the degree of vulcanization for isothermal cure conditions.     

硅橡胶新硫化体系的研究

本文介绍一种硅橡胶新硫化体系,即利用Diels-Alder反应使聚硅氧烷进行交联。所用生胶为含乙烯基的高分子量聚甲基硅氧烷,所用交联剂(硫化剂),即双烯体,系含有环戊二烯基的有机硅化合物。所得弹性体的物理机械性能达到高强度硅橡胶水平。     

硅橡胶/氟橡胶并用胶的制备及力学性能

硅橡胶和氟橡胶作为国防、航天等重要领域的耐热材料一直被人们青睐,但其有着各自地优缺点且价格昂贵,本文尝试将这两种橡胶制成并用胶以解决氟橡胶不耐低温和加工性差的问题,以期增大其使用温度范围。采用机械共混法制备硅橡胶/氟橡胶并用胶,研究了硅橡胶和氟橡胶的混炼工艺、并用比、共硫化体系和硫化条件对并用胶力学性能的影响。结果表明,当硅橡胶/氟橡胶的质量比为10∶90,共硫化体系为3~#硫化剂/过氧化二异丙苯(DCP),一段硫化温度为170℃、硫化压力为10MPa、硫化时间为30min,二段硫化温度为200℃、硫化时间为6h时,并用胶的力学性能达到最好。     

Characterization of sulphur-cured rubbers by high-resolution pyrolysis-gas chromatography with flame photometric detection

Polybutadiene rubber, natural rubber and acrylonitrile-butadiene rubber cured with sulphur and accelerators were characterized by high-resolution pyrolysis-gas chromatography with a sulphur-selective flame photometric detector. With the three polymer systems, various sulphur-containing products characteristic of the base polymers and vulcanization accelerators were observed. The vulcanization process for polybutadiene rubber is discussed on the basis of the relationships between the peak intensities of the characteristic products and cure time.     

Integrated processing-structure-property analysis on rubber in-mold vulcanization

On the basis of the quantitative relationship among rubber processing, structure and property, the methodology of the integrated processing-structure-property analysis on rubber in-mold vulcanization is presented, and then the temporal evolution and spatial distribution characteristics of silicone rubber hot processing parameters, crosslinking structure parameters and mechanical property parameters are obtained by means of the finite element method. The present work is helpful for optimizing curing conditions, and then the design of rubber vulcanization processes according to certain requirements can be done.     

Thermally stable liquid crystalline thermosets based on aromatic copolyesters: Preparation and properties

The synthesis and physical properties are described for a thermally stable liquid crystalline (LC) thermoset based on all aromatic ester units. The persistence of the liquid crystalline phase throughout the curing process was monitored with polarizing optical microscopy. The applicability of these new liquid crystalline thermosets has been evaluated for use as an adhesive for bonding metals, namely titanium. The failure of the adhesive bonds always occurs within the polymer; thus it can be inferred that bonding at the polymer-metal interface is very good. This strong interfacial bonding is attributed to low cure shrinkage and CTE matching of the underlying substrate by the LC resins. The cohesive properties and strength of the cured resin can be greatly enhanced by the addition of filler materials. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35:1061–1067, 1997     

间甲钴黏合体系在轮胎骨架材料中的黏合机理研究

为验证与进一步探索黏合树脂及钴盐对轮胎与镀铜钢丝帘线的增黏作用机理,选取传统黏合树脂R80与2种新型黏合树脂HT1005和H620,通过对2种新型黏合树脂的结构分析、橡胶硫化特性、静态T抽出测试与力学性能测试,并设计了一种新的黏合层强度测试方法与黏合层表征方法,进行机理探索,得出如下结论:含有羟基的极性黏合树脂在橡胶硫化时,会由于与非极性天然橡胶的极性差异产生的热力学不相容从而产生自动相分离,向橡胶与镀铜钢丝的界面层进行迁移汇集,且极性越高迁移能力越强,产生一个介于橡胶与镀铜钢丝之间的树脂富集层.因为黏合树脂交联反应温度为140℃左右,会在天然橡胶硫化反应时发生同步交联反应,黏合树脂形成的网络模量高于橡胶硫化网络,会增强镀铜钢丝与橡胶之间的黏合层强度,并形成一个镀铜钢丝与橡胶之间的模量过渡层,进一步增强黏合层.且极性越强,树脂网络交联程度与橡胶硫化网络交联程度越接近,增黏效果越好;钴盐会活化橡胶中的S,使更多的S迁移到镀铜钢丝表面从生成更多硫化亚铜键,增强黏合.     

Guide for Authors

The effects of epoxidized natural rubber (ENR) on the curing behaviors and adhesive strengths of an epoxy (diglycidyl ether of bisphenol-A) and dicyandiamide/2-methyl imidazole system are studied with differential thermal calorimetry (DSC), scanning electron microscopy (SEM), and Instron tensile testing instrument. From DSC analyses of specimens prepared with unsealed aluminum pans, it is obtained that the reaction exotherm, the time to maximal curing rate, the glass transition temperature, the rate constant, and the reaction order of the epoxy system change with respect to the content of ENR added because of the reaction of ENR with the epoxy system. The results obtained from SEM micrographs indicate that the particle size of the rubber phase increases with increasing the curing temperature and the ENR content. The volume fraction of the separated rubber phase also follows the similar trend except at the high curing temperature which implying that the dissolution of epoxy resin in the ENR phase also depends on the curing temperature and the amount of ENR present. The lap shear strengths of specimens prepared with etched aluminum substrates increase with increasing the curing temperature because of a better cure at a higher temperature, but decrease with increasing the ENR content resulting from an adverse effect of ENR on the mechanical properties of the cured resins.     

Vulcanization kinetics of graphene/styrene butadiene rubber nanocomposites

This paper presents the influence of graphene on the vulcanization kinetics of styrene butadiene rubber （SBR） with dicumyl peroxide. A curemeter and a differential scanning calorimeter were used to investigate the cure kinetics, from which the kinetic parameters and apparent activation energy were obtained. It turns out that with increasing graphene loading, the induction period of the vulcanization process of SBR is remarkably reduced at low graphene loading and then levels off; on the other hand, the optimum cure time shows a monotonous decrease. As a result, the vulcanization rate is suppressed at first and then accelerated, and the corresponding activation energy increases slightly at first and then decreases. Upon adding graphene, the crosslinking density of the nanocomposites increases, because graphene takes part in the vulcanization process.     

Reaction mechanism of halogenated rubber crosslinking using a novel environmentally friendly curing system

Iron (III) acetylacetonate (Fe (acac)) in the presence of triethanolamine (TEOA) was utilized as a novel crosslinking agent for halogenated diene rubber. Following the assumption that the mechanism of the crosslinking bases on the Heck-type reaction mechanism, which requires the presence of a halogen and an unsaturated carbon-carbon double bond, chloroprene rubber (CR) and brominated butyl rubber (BIIR) were utilized as rubber matrices. The results of FTIR spectra analysis confirm the proposed mechanism and indicate that a Heck-type reaction is feasible for performing a crosslinking of halogenated diene rubbers. The use of the Fe (acac)/TEOA curing system results in a significant torque increase during the vulcanization, which confirms the high activity of those compounds. The elimination of halogen from a rubber macromolecular structure or elimination of a basic environment of the crosslinking reaction results in a deactivation of the new curing system.     

Vulcanization kinetics study of natural rubber compounds having different formulation variables

Vulcanization kinetics of natural rubber (NR) compounds with efficient vulcanization system was studied through phenomenological approach using the experimentally cure data obtained from a moving die rheometer. The cure kinetic parameters were defined using the proposed models by Claxton?CLiska and Deng?CIsayev with the support of curve fitting software. The effects of the amount of accelerators, sulfur and silica in the formulations on the cure characteristics and cure kinetic parameters at high cure temperatures were investigated. Kinetic data results showed that the above two models were able to describe the curing behaviour of the studied compounds satisfactorily. It showed that the fitting of the experimental data with Claxton?CLiska and Deng?CIsayev could provide a good platform to investigate the cure kinetics of the prepared NR compounds.     

Effects of cellulose nanocrystals on the vulcanization of natural rubber/cellulose nanocrystals nanocomposite and corresponding regulating strategies

Vulcanization is a vital process in rubber processing, it endows rubber with valuable physical and mechanical properties, making rubber a widely used engineering material. In addition to vulcanization agent, reinforcing fillers play a non-ignorable influence on the vulcanization of rubber nanocomposites. Herein, the effects of cellulose nanocrystals (CNCs) on the vulcanization of natural rubber (NR)/CNCs nanocomposite was studied. It was found that even though the addition of CNCs can effectively improve the dispersion of ZnO in NR matrix, the vulcanization of NR was inhibited. This may be attributed to the CNCs' adsorption of vulcanizing agents (DM, ZnO) and the acidic chemical environment on the surface of CNCs. In order to improve the vulcanization properties of NR/CNCs nanocomposite, tetramethyldithiochloram (TMTD) and triethanolamine (TEOA) were used as a combination accelerator and curing activator, respectively, and polyethylene glycol (PEG) was introduced to screen hydroxyl groups on the surface of CNCs to prohibit the CNCs' adsorption of vulcanizing agents. The results indicate that TMTD and TEOA effectively improved the vulcanization rate of NR/CNCs nanocomposite and increased the crosslink density by an order of magnitude. Subsequently, the tensile strength, tear strength, and so forth. of NR/CNCs nanocomposite were significantly improved. However, PEG hardly help to improve the vulcanization properties of NR/CNCs nanocomposite. In addition, the control samples without CNCs were prepared and characterized, the comparation between NR and NR/CNCs nanocomposite shows that the synergistic effect of crosslink density and CNCs' reinforcement more effectively improve mechanical properties of NR. This work not only elucidates the inhibiting mechanisms of CNCs on the vulcanization of NR, but also provides practical strategies for improving the vulcanization and properties of NR/CNCs nanocomposite. It may accelerate the application of CNCs as rubber reinforcing filler.