Hydrogels are mechanically stabilized through the action of external agents which induce the formation of crosslinks in the polymer network as a consequence of transport and reactive mechanisms. Crosslinking increases the stiffness of the construct, produces inelastic deformations in the polymer network and interacts with the swelling capacity of hydrogels. The control of this process is hence crucial for fulfilling functional criteria in several technological fields, like drug-delivery or bioprinting. Nevertheless, experimental approaches for monitoring the crosslinking kinetics with the required resolution are currently missing. The development of new computational models in the field might open the way to novel investigation tools. This paper presents a thermodynamically consistent chemo-mechanical model in large deformation for reactive–diffusive mechanisms occurring during crosslinking in alginate hydrogels. The system accounts for shrinking and swelling effects, fluid movements, as well as the reaction kinetics of calcium-induced crosslinking. Crosslinks alter mechanical and diffusive properties in the hydrogel. Moreover, on the basis of thermodynamic arguments, internal stresses directly affect the crosslinking kinetics, revealing a two-way coupling between mechanics and chemistry. The model is implemented in a finite element framework, considering a monolithic coupling between chemical transport and mechanics. The computational framework allows characterizing the (experimentally inaccessible) heterogeneous distribution of mechano-chemical quantities and properties in the hydrogel. Parametric campaigns of simulations are presented to investigate hydrogels’ behaviour and compare numerical outcomes with available experimental evidence.

水凝胶通过外部试剂的作用机械稳定，该外部试剂由于运输和反应机理而在聚合物网络中引起交联的形成。交联增加了结构的刚度，在聚合物网络中产生了非弹性变形，并与水凝胶的溶胀能力相互作用。因此，此过程的控制对于在几个技术领域（例如药物递送或生物打印）中满足功能标准至关重要。然而，目前缺少用于以所需的分辨率监测交联动力学的实验方法。在该领域中新计算模型的开发可能会为新颖的调查工具开辟道路。本文提出了藻酸盐水凝胶交联过程中发生的反应扩散机制的大变形热力学一致的化学-机械模型。该系统考虑了收缩和溶胀作用，流体运动以及钙诱导的交联的反应动力学。交联改变了水凝胶中的机械和扩散性能。此外，根据热力学论证，内应力直接影响交联动力学，揭示了力学与化学之间的双向耦合。考虑到化学传输和力学之间的整体耦合，该模型是在有限元框架中实现的。该计算框架允许表征水凝胶中机械化学量和性质的（实验上难以接近的）异质分布。提出了模拟参数运动，以研究水凝胶的行为，并将数值结果与可用的实验证据进行比较。