Coarse-grained simulation of molecular mechanisms of recovery in thermally activated shape-memory polymers

Thermally actuated shape-memory polymers (SMPs) are capable of being programmed into a temporary shape and then recovering their permanent reference shape upon exposure to heat, which facilitates a phase transition that allows dramatic increase in molecular mobility. Experimental, analytical, and computational studies have established empirical relations of the thermomechanical behavior of SMPs that have been instrumental in device design. However, the underlying mechanisms of the recovery behavior and dependence on polymer microstructure remain to be fully understood for copolymer systems. This presents an opportunity for bottom-up studies through molecular modeling; however, the limited time-scales of atomistic simulations prohibit the study of key performance metrics pertaining to recovery. In order to elucidate the effects of phase fraction, recovery temperature, and deformation temperature on shape recovery, here we investigate the shape-memory behavior in a copolymer model with coarse-grained potentials using a two-phase molecular model that reproduces physical crosslinking. Our simulation protocol allows observation of upwards of 90% strain recovery in some cases, at time-scales that are on the order of the timescale of the relevant relaxation mechanism (stress relaxation in the unentangled soft-phase). Partial disintegration of the glassy phase during mechanical deformation is found to contribute to irrecoverable strain. Temperature dependence of the recovery indicates nearly full elastic recovery above the trigger temperature, which is near the glass-transition temperature of the rubbery switching matrix. We find that the trigger temperature is also directly correlated with the deformation temperature, indicating that deformation temperature influences the recovery temperatures required to obtain a given amount of shape recovery, until the plateau regions overlap above the transition region. Increasing the fraction of glassy phase results in higher strain recovery at low to intermediate temperatures, a widening of the transition region, and an eventual crossover at high temperatures. Our results corroborate experimental findings on shape-memory behavior and provide new insight into factors governing deformation recovery that can be leveraged in biomaterials design. The established computational methodology can be extended in straightforward ways to investigate the effects of monomer chemistry, low-molecular-weight solvents, physical and chemical crosslinking, different phase-separation morphologies, and more complicated mechanical deformation toward predictive modeling capabilities for stimuli-responsive polymers.     

Finite element modelling of rubber-like polymers based on chain statistics

In this work finite element simulations are conducted based on the micro structure of polymers in order to transfer the information of the micro level to the macro level. The micro structure of polymers is characterized by chain-like macromolecules linked together at certain points. In this way an irregular three-dimensional network is formed. Many authors use the tool of statistical mechanics to describe the deformation behaviour of the entire network. Most of these concepts can be reformulated as traditional continuum mechanical formulations. They are, however, restricted to affine deformation, regular chain arrangements and purely elastic material behaviour. For this reason, in the present contribution, we propose a new finite element-based simulation method for polymer networks which enables us to include non-affinity and arbitrary chain configurations. It can be easily extended to include chain breakage and reconnection.The polymer structure to be investigated, e.g. a rubber boot or a seal, is discretized by means of tetrahedral elements. To each edge of a tetrahedral element one truss element is attached which models the force–stretch behaviour of a bundle of polymer chains. Each of these tetrahedral unit cells represents the micro mechanical material behaviour in a certain point of the network. The proposed method provides the possibility to observe how changes at the microscopic level influence the macroscopic material behaviour. Such information is especially valuable for the polymer industry.     

Hyperelastic model for polyacrylamide-gelatin double network shape-memory hydrogels

A shape-memory double network hydrogel consists of two polymer networks: a chemically crosslinked primary network that is responsible for the permanent shape and a physically crosslinked secondary network that is used to fix the temporary shapes. The formation/melting transition of the secondary network serves as an effective mechanism for the double network hydrogel's shape-memory effect. When the crosslinks in the secondary network are dissociated by applying an external stimulus, only the primary network is left to support the load. When the secondary network is re-formed by removing the stimulus, both the primary and secondary networks support the load. In the past, models have been developed for the constitutive behaviors of double network hydrogels, but the model of shape-memory double network hydrogels is still lacking. This work aims to build a constitutive model for the polyacrylamide-gelatin double network shape-memory hydrogel developed in our previous work. The model is first calibrated by experimental data of the double network shape-memory hydrogel under uniaxial loading and then employed to predict the shape-fixing performance of the hydrogel. The model is also implemented into a three-dimension finite element code and utilized to simulate the shape-memory behavior of the double network hydrogel with inhomogeneous deformations related to applications.

Graphic abstract

A shape-memory double network hydrogel consists of a chemically crosslinked primary network and a physically crosslinked secondary network. The formation/melting transition of the secondary network serves as an effective mechanism for the shape-memory effect of the double network hydrogel. This work built a constitutive model for the polyacrylamide-and-gelatin double network shape-memory hydrogel. The model was first calibrated by experimental data and then employed to predict the shape-fixing performance of the hydrogel. The model was also implemented into a three-dimension finite element code and utilized to simulate the shape-memory behavior of double network hydrogel in complex geometries.

     

Photo-induced deformation of active polymer films: Single spot irradiation

Light-activated polymers can undergo complex deformation in response to the combination of mechanical and optical stimuli. These materials are attractive for remote actuation and sensing applications. However, the behavior of such materials subjected to photomechanical patterning is not well understood. In this paper we consider a polymer that operates by photoactivated stress relaxation; at the molecular level, photoinitiation of residual initiator molecules generate free radicals that break and then reform in-chain functionalities of stretched chains in an elastomeric network, which results in macroscopic stress relaxation. We carry out experiments and finite element calculations that demonstrate the sequence of deformation events culminating in the formation of a buckled spot as a result of biaxially stretching the elastomeric film then irradiating a circular region followed by releasing the mechanical constraint. In order to better understand the photomechanics, we analyze a simpler model problem wherein a linear elastic, stress relaxing disk is subjected to (i) radial extension, (ii) irradiation of a concentric circular region, and (iii) release of the applied displacements in (i), which results in deformation and stress redistribution. In the final step, the deformation may transition from planar to buckling out of the plane depending on system parameters. Companion finite element calculations are performed against which our analytical results are in good agreement. Although not directly comparable, the analytic model qualitatively agrees with the experiments. The results of this work provide a useful foundation from which to explore more interesting behavior of periodically photo-mechanically patterned films and other more challenging actuation problems.     

Phenomenological modeling of viscous electrostrictive polymers

A common usage for electroactive polymers (EAPs) is in different types of actuators, where advantage is taken of the deformation of the polymer due to an electric field. It turns out that time-dependent effects are present in these applications. One of these effects is the viscoelastic behavior of the polymer material. In view of the modeling and simulation of applications for EAP within a continuum mechanics setting, a phenomenological framework for an electro-viscoelastic material model is elaborated in this work. The different specific models are fitted to experimental data available in the literature. While the experimental data used for inherent electrostriction is restricted to small strains, a large strain setting is used for the model in order to account for possible applications where the polymers undergo large deformations, such as in pre-strained actuators.     

Fluid–structure interactions of photo-responsive polymer cantilevers

A new class of photomechanical liquid crystal networks (LCNs) has emerged, which generate large bending deformation and fast response times that scale with the resonance of the polymer films. Here, a numerical study is presented that describes the photomechanical structural dynamic behavior of an LCN in a fluid medium; however, the methodology is also applicable to fluid–structure interactions of a broader range of adaptive structures. Here, we simulate the oscillation of photomechanical cantilevers excited by light while simultaneously modeling the effect of the surrounding fluid at different ambient pressures. The photoactuated LCN is modeled as an elastic thin cantilever plate, and gradients in photostrain from the external light are computed from the assumptions of light absorption and photoisomerization through the film thickness. Numerical approximations of the equations governing the plate are based on cubic B-spline shape functions and a second order implicit Newmark central scheme for time integration. For the fluid, three dimensional unsteady incompressible Navier–Stokes equations are solved using the arbitrary Lagrangian–Eulerian (ALE) method, which employs a structured body-fitted curvilinear coordinate system where the solid–fluid interface is a mesh line of the system, and the complicated interface boundary conditions are accommodated in a conventional finite-volume formulation. Numerical examples are given which provide new insight into material behavior in a fluid medium as a function of ambient pressure.     

Micromechanics, macromechanics and constitutive modeling of the elasto-viscoplastic deformation of rubber-toughened glassy polymers

Under certain conditions, such as sufficiently low temperatures, high loading rates and/or highly triaxial stress states, glassy polymers display an unfavorable characteristic—brittleness. A technique used for reducing the brittleness (increasing the fracture toughness) of these materials is rubber toughening. While there is significant qualitative understanding of the mechanical behavior of rubber-toughened polymers, quantitative modeling tools for the large-strain deformation of rubber-toughened glassy polymers are largely lacking.In this paper, we develop a suite of numerical tools to investigate the mechanical behavior of rubber-toughened glassy polymers, with emphasis on rubber-toughened polycarbonate. The rubber particles are modeled as voids in view of their deformation-induced cavitation early during deformation. A three-dimensional micromechanical model of the heterogeneous microstructure is developed to study the effects of initial rubber particle (void) volume fraction on the underlying elasto-viscoplastic deformation mechanisms in the material, and how these mechanisms influence the macroscopic response of the material. A continuum-level constitutive model is developed for the large-strain elasto-viscoplastic deformation of porous glassy polymers, and it is calibrated against micromechanical modeling results for porous polycarbonate. The constitutive model can be used to study various boundary value problems involving rubber-toughened (porous) glassy polymers. As an example, the case of an axisymmetric notched bar is simulated for the case of polycarbonate with varying levels of initial porosity. The quality of the constitutive model calibration is assessed using a multi-scale modeling approach.     

A constitutive theory for shape memory polymers. Part I: Large deformations

A constitutive theory is developed for shape memory polymers. It is to describe the thermomechanical properties of such materials under large deformations. The theory is based on the idea, which is developed in the work of Liu et al. [2006. Thermomechanics of shape memory polymers: uniaxial experiments and constitutive modeling. Int. J. Plasticity 22, 279-313], that the coexisting active and frozen phases of the polymer and the transitions between them provide the underlying mechanisms for strain storage and recovery during a shape memory cycle. General constitutive functions for nonlinear thermoelastic materials are used for the active and frozen phases. Also used is an internal state variable which describes the volume fraction of the frozen phase. The material behavior of history dependence in the frozen phase is captured by using the concept of frozen reference configuration. The relation between the overall deformation and the stress is derived by integration of the constitutive equations of the coexisting phases. As a special case of the nonlinear constitutive model, a neo-Hookean type constitutive function for each phase is considered. The material behaviors in a shape memory cycle under uniaxial loading are examined. A linear constitutive model is derived from the nonlinear theory by considering small deformations. The predictions of this model are compared with experimental measurements.     

Interfacial welding of dynamic covalent network polymers

Dynamic covalent network (or covalent adaptable network) polymers can rearrange their macromolecular chain network by bond exchange reactions (BERs) where an active unit replaces a unit in an existing bond to form a new bond. Such macromolecular events, when they occur in large amounts, can attribute to unusual properties that are not seen in conventional covalent network polymers, such as shape reforming and surface welding; the latter further enables the important attributes of material malleability and powder-based reprocessing. In this paper, a multiscale modeling framework is developed to study the surface welding of thermally induced dynamic covalent network polymers. At the macromolecular network level, a lattice model is developed to describe the chain density evolution across the interface and its connection to bulk stress relaxation due to BERs. The chain density evolution rule is then fed into a continuum level interfacial model that takes into account surface roughness and applied pressure to predict the effective elastic modulus and interfacial fracture energy of welded polymers. The model yields particularly accessible results where the moduli and interfacial strength of the welded samples as a function of temperature and pressure can be predicted with four parameters, three of which can be measured directly. The model identifies the dependency of surface welding efficiency on the applied thermal and mechanical fields: the pressure will affect the real contact area under the consideration of surface roughness of dynamic covalent network polymers; the chain density increment on the real contact area of interface is only dependent on the welding time and temperature. The modeling approach shows good agreement with experiments and can be extended to other types of dynamic covalent network polymers using different stimuli for BERs, such as light and moisture etc.     

Rheological study of multilayer functionalized polymers: characterization of interdiffusion and reaction at polymer/polymer interface

Rheological behavior in molten state of multilayered polymers was investigated by dynamic mechanical measurements. The competition between polymer/polymer interdiffusion and interfacial reaction of functionalized polymers in a sandwich structure was followed by oscillatory mode under small amplitudes of deformation. The systems chosen for study were polyethylene (PE) grafted with glycidyl methacrylate/polyamide (PA) 6 as a reactive system and PE/PA6 as nonreactive one. Moreover, the interphase thickness was estimated by using thermodynamical models. Experimental results of bilayer systems were compared to existing models of multiphase systems. An expression of storage modulus as a function of welding time was also suggested. Thus, the fit between this one and the experimental data was satisfactory with the different appearing phenomena.     

Modelling large deformation behaviour under loading–unloading of semicrystalline polymers: Application to a high density polyethylene

In this work, the large deformation behaviour under monotonic loading and unloading of a high density polyethylene (HDPE) is studied. To analyze the nonlinear time-dependent response of the material, mechanical tests were conducted at room temperature under constant true strain rates and stress relaxation conditions. A physically-based inelastic model written under finite strain formulation is proposed to describe the mechanical behaviour of HDPE. In the model, the inelastic mechanisms involve two parallel elements: a visco-hyperelastic network resistance acting in parallel with a viscoelastic–viscoplastic intermolecular resistance where the amorphous and crystalline phases are explicitly taken into consideration. The semicrystalline polymer is considered as a two-phase composite. The influence of the crystallinity on the loading and unloading behaviour is investigated. Numerical results are compared to experimental data. It is shown that the model is able to accurately reproduce the experimental observations corresponding to monotonic loading, unloading and stress relaxation behaviours at different strain levels. Finally, the model capabilities to capture cyclic loading–unloading behaviour up to large strains are discussed. To demonstrate the improved modelling capabilities, simulations are also performed using the original model of Boyce et al. [Boyce, M.C., Socrate, S., Llana, P.G., 2000. Constitutive model for the finite deformation stress–strain behavior of poly(ethylene terephthalate) above the glass transition. Polymer 41, 2183–2201] modified by Ahzi et al. [Ahzi, S., Makradi, A., Gregory, R.V., Edie, D.D., 2003. Modeling of deformation behavior and strain-induced crystallization in poly(ethylene terephthalate) above the glass transition temperature. Mechanics of Materials 35, 1139–1148].     

Primitive chain network simulations for branched polymers

We present simulations of branched polymer dynamics based on a sliplink network model, which also accounts for topological change around branch points, i.e., for branch-point diffusion. It is well-known that, with the exception of stars, branched polymers may show a peculiar rheological behavior due to the exceptionally slow relaxation of the backbone chains bridging branch points. Though Brownian simulations based on sliplinks are powerful tools to study the motion of polymers and to predict rheological properties, none of the existing methods can simulate the relaxation of the bridge chains. The reason for that is lack of a rule for network topology rearrangement around branch points, so that entanglements between bridge chains cannot be renewed. Therefore, we introduce in this paper one possible branch-point mobility rule into our primitive chain network model. For star polymers, diffusion coefficients were calculated and compared with experiments. For both star and H-shaped polymers, diffusion was simulated both with and without the new rule, and the effect on linear viscoelasticity was also determined in one case.     

Modelling the curing process in magneto-sensitive polymers: Rate-dependence and shrinkage

This paper deals with a phenomenologically motivated magneto-viscoelastic coupled finite strain framework for simulating the curing process of polymers under the application of a coupled magneto-mechanical load. Magneto-sensitive polymers are prepared by mixing micron-sized ferromagnetic particles in uncured polymers. Application of a magnetic field during the curing process causes the particles to align and form chain-like structures lending an overall anisotropy to the material. The polymer curing is a viscoelastic complex process where a transformation from fluid to solid occurs in the course of time. During curing, volume shrinkage also occurs due to the packing of polymer chains by chemical reactions. Such reactions impart a continuous change of magneto-mechanical properties that can be modelled by an appropriate constitutive relation where the temporal evolution of material parameters is considered. To model the shrinkage during curing, a magnetic-induction-dependent approach is proposed which is based on a multiplicative decomposition of the deformation gradient into a mechanical and a magnetic-induction-dependent volume shrinkage part. The proposed model obeys the relevant laws of thermodynamics. Numerical examples, based on a generalised Mooney–Rivlin energy function, are presented to demonstrate the model capacity in the case of a magneto-viscoelastically coupled load.     

The effect of large deformation and material nonlinearity on gel indentation

A gel, an aggregate of polymers with solvents, has dual attributes of solid and liquid as solvent migrates in and out of the polymer network. Indentation has recently been used to characterize the mechanical properties of gels. This paper evaluates the effects of large deformation and material nonlinearity on gel indentation through theoretical modeling and finite element analysis. It is found that large deformation significantly affects the interpretation of the experimental observations and the classical relation between indentation force and depth has limitations for large deformation. The material nonlinearity does not play a very important role on indentation experiment so that the poroelasticity is a good approximation. Based on these observations, this paper proposes an alternative approach to measure the mechanical properties of gels, namely, uniaxial compression experiment.     

A generalized coupled viscoplastic-viscodamage-viscohealing theory for glassy polymers

A thermodynamic consistent, small-strain, non-unified model is developed to capture the irregular rate dependency included in the strain controlled inelastic responses of polymers at the glassy state. The model is considered as a generalized Frederick-Armstrong-Philips-Chaboche (FAPC) theory proposed by [Voyiadjis and Basuroychowdhury, 1998] and [Voyiadjis and Abu Al-Rub, 2003] which is based on a von Mises and Chaboche isotropic hardening type viscoplasticity formulation. Using the proposed model, different experimental results are simulated and the range of viscoplastic related material constants are obtained through a parametric study. The thermodynamic framework is used to incorporate the effect of coupling between viscodamage and viscohealing phenomena into the inelastic deformation of glassy polymers. This coupling effect is crucial for polymeric based self healing systems in which different damage mechanisms are active and the efficiency of the healing processes are highly dependent on the damage. The computational aspect for general coupled inelastic-damage-healing processes together with the required solution algorithms are elaborated and the inelastic-damage-healing response of a polymeric based self-healing system is simulated. The proposed viscoplasticity theory constitutes a physically consistent approach to model the irregular mechanical responses of glassy polymers and the viscodamage model provides an exquisite predicting tool to evaluate the ductile damage associated with the large inelastic deformation and low cycle fatigue in polymeric based material systems. In conclusion, a well structured viscohealing theory is formulated for polymeric based self healing systems.     

Non-elliptic elastic materials and the modeling of dissipative mechanical behavior: an example

In the context of a special problem, this paper investigates the possibility of modeling dissipative mechanical response in solids on the basis of the equilibrium theory of finite elasticity for materials that may lose ellipticity at large strains. Quasi-static motions for such materials are in general dissipative if the associated equilibrium fields involve discontinuous displacement gradients. For the problem treated, consideration of such deformations is shown to lead naturally to an internal variable formalism similar to those used to describe macroscopic plastic behavior arising from microstructural effects. For quasi-static motions which are maximally dissipative in a specified sense, this formalism leads to a mechanical response which resembles that associated with the pseudo-elastic effect in shape-memory alloys.     

Simulation of strain-induced anisotropy for polymers with weighting functions

The alignment of polymer chains is a well-known microstructural evolution effect due to straining of polymers. This has a drastic influence on the macroscopic properties of the initially isotropic material, such as a pronounced strength in the loading direction of stretched films. For modeling the effect of strain-induced anisotropy, a macroscopic constitutive model is developed in this paper. Within a thermodynamic framework, an additive decomposition of the logarithmic Hencky strain tensor into elastic and inelastic parts is used to formulate the constitutive equations. As a key idea, weighting functions are introduced to represent a strain-softening/hardening effect to account for induced anisotropy. These functions represent the ratio between the total strain rate (representing the actual loading direction) and a structural tensor (representing the stretched polymer chains). In this way, we introduce material parameters as a sum of weighted direction-related quantities. The numerical implementation of the resulting set of constitutive is used to identify material parameters based on experimental data, exhibiting strain-induced anisotropy. In the finite-element examples, we simulate the cold-forming of amorphous thermoplastic films below the glass transition temperature subjected to different re-loading directions.     

Electroelasticity of polymer networks

A multiscale analysis of the electromechanical coupling in elastic dielectrics is conducted, starting from the discrete monomer level through the polymer chain and up to the macroscopic level. Three models for the local relations between the molecular dipoles and the electric field that can fit a variety of dipolar monomers are considered. The entropy of the network is accounted for within the framework of statistical mechanics with appropriate kinematic and energetic constraints. At the macroscopic level closed-form explicit expressions for the behaviors of amorphous dielectrics and isotropic polymer networks are determined, none of which admits the commonly assumed linear relation between the polarization and the electric field. The analysis reveals the dependence of the macroscopic coupled behavior on three primary microscopic parameters: the model assumed for the local behavior, the intensity of the local dipole, and the length of the chain. We show how these parameters influence the directional distributions of the monomers and the hence the resulting overall response of the network. In particular, the dependences of the polarization and the polarization induced stress on the deformation of the dielectric are illustrated. More surprisingly, we also reveal a dependence of the stress on the electric field which stems from the kinematic constraint imposed on the chains.