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引用次数: 0
摘要
当空间局部聚合反应垂直于重力场运动时,热锋聚合(FP)中的温度梯度产生浮力驱动对流。我们提出了绝热条件下系统动力学的理论研究。聚合物和反应物混合物被认为处于相同的液相,但粘度会随着聚合程度的增加而增加。我们发现,在垂直和水平方向上,反应区以一个类似热点的模式传播,对称性被打破。此外,系统可以达到渐近动力学特征,其特征是具有稳定形状的锋面以恒定速度传播,周围有稳定的涡旋。随着涡旋强度的增加,无论是通过降低反应物的粘度还是通过增加层的厚度,我们观察到(i)由纯反应扩散和流体动力学模型预测的被动状态和(ii)主动化学流体动力学状态之间的过渡,这些模型分别崩溃。在活动区(ii),锋面速度随着对流的增强而减小。通过尺度分析,我们解释了水动力流如何降低聚合波的速度。正如最近在固液FP实验中观察到的那样,随着聚合物粘度的增大,流动被转移到反应区前面,相对于体系的中间变得更加对称。Gao et al.,物理学。中国生物医学工程学报,2003,11(2):481 - 481。[j].热传学报,2016,33(5):626 - 626。
Frontal polymerization in thin layers: Hydrodynamic effects and asymptotic dynamics.
Buoyancy-driven convection currents arise from temperature gradients in thermal frontal polymerization (FP) when the spatially localized polymerization reaction travels perpendicularly to the gravity field. We propose a theoretical study of the system dynamics under adiabatic conditions. The polymer and the reactant mixture are considered to be in the same liquid phase, but the viscosity can increase with the degree of polymerization. We find that the reaction zone propagates as a hot spot-like pattern with a broken symmetry in both the vertical and horizontal directions. Furthermore, the system can reach an asymptotic dynamics characterized by a front with a steady shape that propagates at constant speed with a steady vortex surrounding it. As the strength of the vortex is increased, either by decreasing the reactants' viscosity or by increasing the layer's thickness, we observe a transition between (i) a passive regime predicted by pure reaction-diffusion and hydrodynamic models and (ii) an active chemo-hydrodynamic regime where such models separately break down. In the active regime (ii), the front speed decreases as convection intensifies. By means of a scaling analysis, we explain how hydrodynamic currents might lower the velocity of a polymerization wave. As the viscosity of the polymer is enlarged, the flow is shifted ahead of the reaction zone and becomes more symmetrical with respect to the middle of the system, as recently observed in solid-liquid FP experiments [Y. Gao et al., Phys. Rev. Lett. 130, 028101 (2023) and Y. Gao et al., Int. J. Heat Mass Transf. 240, 126622 (2025)].
期刊介绍:
The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance.
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Atoms, Molecules, and Clusters
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