Ye Sheng, Cramer Neil B, Stevens Blake E, Sani Robert L, Bowman Christopher N
Department of Chemical & Biological Engineering, University of Colorado, UCB 424, Boulder, CO 80309.
Macromolecules. 2011 Jun 28;44(12):4988-4996. doi: 10.1021/ma200098e.
Induction curing is demonstrated as a novel type of in situ radiation curing that maintains most of the advantages of photocuring while eliminating the restriction of light accessibility. Induction curing is utilized to polymerize opaque composites comprised of thiol-acrylate and thiol-ene resins, nanoscale magnetic particles, and carbon nanotubes. Nanoscale magnetic particles are dispersed in the resin and upon exposure to the magnetic field, these particles lead to induction heating that rapidly initiates the polymerization. Heat transfer profiles and reaction kinetics of the samples are modeled during the reactions with varying induction heater power, species concentration, species type and sample thickness, and the model is compared with the experimental results. Thiol-ene polymerizations achieved full conversion between 1.5 minutes and 1 hour, depending on the field intensity and the composition, with the maximum reaction temperature decreasing from 146 - 87 °C when the induction heater power was decreased from 8 - 3 kW. The polymerization reactions of the thiol-acrylate system were demonstrated to achieve full conversion between 0.6 and 30 minutes with maximum temperatures from 139 to 86 °C. The experimental behavior was characterized and the temperature profile modeled for the thiol-acrylate composite comprised of sub100nm nickel particles and induction heater power in the range of 32 to 20 kW. A 9°C average deviation was observed between the modeling and experimental results for the maximum temperature rise. The model also was utilized to predict reaction temperatures and kinetics for systems with varying thermal initiator concentration, initiator half-life, monomer molecular weight and temperature gradients in samples with varying thickness, thereby demonstrating that induction curing represents a designable and tunable polymerization method. Finally, induction curing was utilized to cure thiol-acrylate systems containing carbon nanotubes where 1 wt% carbon nanotubes resulted in systems where the storage modulus increased from 17.6 ± 0.2 to 21.6 ± 0.1 MPa and an electrical conductivity that increased from <10(-7) to 0.33 ± 0.5 S/m.
感应固化被证明是一种新型的原位辐射固化方式,它保留了光固化的大部分优点,同时消除了光可达性的限制。感应固化用于使由硫醇 - 丙烯酸酯和硫醇 - 烯树脂、纳米级磁性颗粒和碳纳米管组成的不透明复合材料聚合。纳米级磁性颗粒分散在树脂中,在暴露于磁场时,这些颗粒会导致感应加热,从而迅速引发聚合反应。在反应过程中,针对不同的感应加热器功率、物种浓度、物种类型和样品厚度,对样品的传热曲线和反应动力学进行建模,并将该模型与实验结果进行比较。硫醇 - 烯聚合反应在1.5分钟至1小时内实现完全转化,具体取决于场强和组成,当感应加热器功率从8千瓦降至3千瓦 时,最高反应温度从146℃降至87℃。硫醇 - 丙烯酸酯体系的聚合反应在0.6至30分钟内实现完全转化,最高温度为139至86℃。对由亚100纳米镍颗粒和功率在32至20千瓦范围内的感应加热器组成的硫醇 - 丙烯酸酯复合材料的实验行为进行了表征,并对温度曲线进行了建模。对于最高温度上升,建模结果与实验结果之间观察到9℃的平均偏差。该模型还用于预测具有不同热引发剂浓度、引发剂半衰期、单体分子量以及不同厚度样品中温度梯度的体系的反应温度和动力学,从而证明感应固化是一种可设计和可调谐的聚合方法。最后,感应固化用于固化含有碳纳米管的硫醇 - 丙烯酸酯体系,其中1 wt%的碳纳米管使体系的储能模量从17.6±0.2兆帕增加到21.6±0.1兆帕,电导率从<10(-7)增加到0.33±0.5 S/m。