Self-Healing of Unentangled Polymer Networks with Reversible Bonds.
Self-Healing of Unentangled Polymer Networks with Reversible Bonds.
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DOI：
10.1021/ma401111n
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发表时间：
2013-09-24
期刊：
影响因子：
5.5
通讯作者：
Rubinstein, Michael
中科院分区：
文献类型：
--
作者：
Stukalin, Evgeny B.;Cai, Li-Heng;Kumar, N. Arun;Leibler, Ludwik;Rubinstein, Michael
自修复聚合物材料是一种损伤后可以恢复到原始状态并完全或部分恢复机械强度的系统。利用标度理论，我们研究了一个简单的无纠缠聚合物网络自主自愈模型。在该模型中，每个聚合物链的两个末端单体中的一个固定在空间中，模仿挂在聚合物网络上的悬挂链，而每个链另一端的粘性单体可以与另一链的粘性端形成成对的可逆键。我们在这个简单的模型中研究了可逆键的反应动力学，并分析了自修复过程中的不同阶段。在断裂面保持分离的较短等待时间后，在愈合期间跨越断裂面的桥的形成和材料强度的恢复明显更快。我们观察到，与自愈相比，当两个裸露的表面接触时，与自愈相比，开放贴片的平衡(非常低)密度时，自粘接桥的形成速度最慢。在短等待时间下，异常扩散在材料自修复中起主要作用，而在长等待时间下，通过断裂界面的粘结恢复是由于粘合剂在不同粘结伙伴之间的跳跃扩散所致。与自粘合相比，桥接形成中的自愈加速是由于开放贴纸的非平衡浓度过高。断裂界面上可逆键的完全恢复(桥的形成)发生在比整体可逆键浓度的平衡时间稍长的时间之后。
Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of unentangled polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess non-equilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk.
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