Thermomechanical behavior of thermoset shape memory polymer programmed by cold-compression: Testing and constitutive modeling

Programming is a key process for thermally activated stress or strain recovery of shape memory polymers (SMPs). Typically, programming requires an initial heating above the glass transition temperature (T_g), subsequent cooling below T_g and removal of the applied load, in order to fix a temporary shape. This work adopted a new approach to program thermoset SMPs directly at temperatures well below T_g, which effectively simplified the shape fixing process. 1-D compression programming below T_g and free shape recovery of a thermoset SMP were experimentally investigated. Functional stability of the shape fixity under various environmental attacks was also experimentally evaluated. A mechanism-based thermoviscoelastic-thermoviscoplastic constitutive model incorporating structural and stress relaxation was then developed to predict the nonlinear shape memory behavior of the SMP trained below T_g. Comparison between the prediction and the experiment showed good agreement. The structure dependence of the thermomechanical behavior of the SMP was further discussed through a parametric study per the validated constitutive model. This study validates that programming by cold-compression is a viable alternative for thermally responsive thermoset SMPs.     

Thermomechanics of shape memory polymers: Uniaxial experiments and constitutive modeling

Shape memory polymers (SMPs) can retain a temporary shape after pre-deformation at an elevated temperature and subsequent cooling to a lower temperature. When reheated, the original shape can be recovered. Relatively little work in the literature has addressed the constitutive modeling of the unique thermomechanical coupling in SMPs. Constitutive models are critical for predicting the deformation and recovery of SMPs under a range of different constraints. In this study, the thermomechanics of shape storage and recovery of an epoxy resin is systematically investigated for small strains (within ±10%) in uniaxial tension and uniaxial compression. After initial pre-deformation at a high temperature, the strain is held constant for shape storage while the stress evolution is monitored. Three cases of heated recovery are selected: unconstrained free strain recovery, stress recovery under full constraint at the pre-deformation strain level (no low temperature unloading), and stress recovery under full constraint at a strain level fixed at a low temperature (low temperature unloading). The free strain recovery results indicate that the polymer can fully recover the original shape when reheated above its glass transition temperature (T_g). Due to the high stiffness in the glassy state (T < T_g), the evolution of the stress under strain constraint is strongly influenced by thermal expansion of the polymer. The relationship between the final recoverable stress and strain is governed by the stress–strain response of the polymer above T_g. Based on the experimental results and the molecular mechanism of shape memory, a three-dimensional small-strain internal state variable constitutive model is developed. The model quantifies the storage and release of the entropic deformation during thermomechanical processes. The fraction of the material freezing a temporary entropy state is a function of temperature, which can be determined by fitting the free strain recovery response. A free energy function for the model is formulated and thermodynamic consistency is ensured. The model can predict the stress evolution of the uniaxial experimental results. The model captures differences in the tensile and compressive recovery responses caused by thermal expansion. The model is used to explore strain and stress recovery responses under various flexible external constraints that would be encountered in applications of SMPs.     

A finite deformation thermomechanical constitutive model for triple shape polymeric composites based on dual thermal transitions

Shape memory polymers (SMPs) have gained strong research interests recently due to their mechanical action that exploits their capability to fix temporary shapes and recover their permanent shape in response to an environmental stimulus such as heat, electricity, irradiation, moisture or magnetic field, among others. Along with interests in conventional “dual-shape” SMPs that can recover from one temporary shape to the permanent shape, multi-shape SMPs that can fix more than one temporary shapes and recover sequentially from one temporary shape to another and eventually to the permanent shape, have started to attract increasing attention. Two approaches have been used to achieve multi-shape shape memory effects (m-SMEs). The first approach uses polymers with a wide thermal transition temperature whilst the second method employs multiple thermal transition temperatures, most notably, uses two distinct thermal transition temperatures to obtain triple-shape memory effects (t-SMEs). Recently, one of the authors’ group reported a triple-shape polymeric composite (TSPC), which is composed of an amorphous SMP matrix (epoxy), providing the system the rubber-glass transition to fix one temporary shape, and an interpenetrating crystallizable fiber network (PCL) providing the system the melt-crystal transition to fix the other temporary shape. A one-dimensional (1D) material model developed by the authors revealed the underlying shape memory mechanism of shape memory behaviors due to dual thermal transitions. In this paper, a three-dimension (3D) finite deformation thermomechanical constitutive model is presented to enable the simulations of t-SME under more complicated deformation conditions. Simple experiments, such as uniaxial tensions, thermal expansions and stress relaxation tests were carried out to identify parameters used in the model. Using an implemented user material subroutine (UMAT), the constitutive model successfully reproduced different types of shape memory behaviors exhibited in experiments designed for shape memory behaviors. Stress distribution analyses were performed to analyze the stress distribution during those different shape memory behaviors. The model was also able to simulate complicated applications, such as a twisted sheet and a folded stick, to demonstrate t-SME.     

Segmental orientation in plastically deformed glassy PMMA

In this study, spatial orientational distribution functions of labeled chain segments of cross-linked and linear PMMA were obtained by solid-state NMR as a function of finite deformation (far) below and (far) above the glass transition temperature T_g. The applied data analysis allows comparison of theoretical predictions and experimental data, both in terms of the orientational probability distributions as a function of two polar angles, as well as in terms of moments of the distribution. Orientation-strain relationships of chain segments agreed above and below T_g with predictions from the rubber-elastic affine network model, but suggests a much denser network below T_g than given by the cross-link density or the entanglement density in the melt. This suggested network structure is believed to be the generator of segmental orientation during plastic deformation in the glassy state, independent of the range of applied cross-link densities and deformation rates used in this study.     

Predicting thermal shape memory of crosslinked polymer networks from linear viscoelasticity

The viscoelastic behavior of an amorphous shape memory polymer network and its dependence on time and temperature were measured by dynamic mechanical analysis. The resulting thermo-mechanical behavior was modeled and implemented in a commercial finite element code. The ability of the resulting thermomechanical model to simulate and, eventually, predict the shape storage and shape recovery of the material was evaluated against experimental shape memory thermomechanical torsion data in a large deformation regimen. The simulations showed excellent agreement with experimental shape memory thermomechanical cycle data. This demonstrates the dependence of the shape recovery on time and temperature. The results suggest that accurate predictions of the shape recovery of any amorphous polymer networks under any thermomechanical conditions combination solely depends on considering the material viscoelasticity and its time–temperature dependence.     

A thermoviscoelastic model for amorphous shape memory polymers: Incorporating structural and stress relaxation

A thermoviscoelastic constitutive model is developed for amorphous shape memory polymers (SMP) based on the hypothesis that structural and stress relaxation are the primary molecular mechanisms of the shape memory effect and its time-dependence. This work represents a new and fundamentally different approach to modeling amorphous SMPs. A principal feature of the constitutive model is the incorporation of the nonlinear Adam–Gibbs model of structural relaxation and a modified Eyring model of viscous flow into a continuum finite–deformation thermoviscoelastic framework. Comparisons with experiments show that the model can reproduce the strain–temperature response, the temperature and strain-rate dependent stress–strain response, and important features of the temperature dependence of the shape memory response. Because the model includes structural relaxation, the shape memory response also exhibits a dependence on the cooling and heating rates.     

Hysteresis modeling of two-way shape memory effect in NiTi alloys

In the present study the two-way shape memory effect (TWSME) of a Ni-51 at.% Ti alloy was investigated and a numerical model, able to simulate its hysteretic behaviour in the strain-temperature response, is proposed. In particular, the TWSME was induced through a proper thermo-mechanical training, carried out at increasing number of training cycles and for two values of training deformation, and the thermal hysteretic behaviour, between M _f (Martensite finish temperature) and A _f (Austenite finish temperature), was recorded. The experimental measurements were used to develop a phenomenological model, based on the Prandtl-Ishlinksii hysteresis operator, which was implemented in a Matlab^® function and a Simulink^® model. A systematic comparison between experimental results and numerical predictions is illustrated and a satisfactory accuracy and efficiency has been observed, therefore the method looks suitable for real-time control of NiTi based actuators.     

Viscosity and dynamics of nanorod (carbon nanotubes, cellulose whiskers, stiff polymers and polymer fibers) suspensions

The zero shear viscosity and the dynamic behaviors of different nanorod dispersions (carbon nanotubes (CNTs), cellulose whiskers, polymer nanofibers, crosslinked polymer nanofibers, and stiff polymers such as poly(γ-benzyl-α-l-glutamate) (PBLG)) were compared and discussed from literature data. Their Brownian dynamic behaviors have always been discussed in the frame of the Doi–Edwards theory. In agreement with this theory, the straight rigid rods (CNTs, cellulose whisker, polymer nanofibers) obey a master curve in the reduced viscosity (or rotary diffusivity) c power laws on viscosity (η ₀ ∝ φ ³) and diffusivity (D _r ∝ ? ^?2). On the contrary, stiff polymer chains and crosslinked polymer fibers at temperature above T _g exhibit different and two distinct dynamic behaviors. Despite their deviation from the ideal rigidity, surprisingly it can be noted that stiff polymers such as PBLG have been extremely used in the literature to verify the Doi–Edwards theory. Finally, flexible crosslinked chains at T > T _g , do not obey the Doi–Edwards theory, and their dynamics are close to the physics of polymer solutions in terms of power laws.     

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.     

水蒸汽驱动高聚物形状记忆效应的力学模拟

部分形状记忆高聚物在相对湿度较高的环境中会从其临时形状恢复到永久形状,这种效应被称之为水蒸汽驱动形状记忆效应。由于不需要升高温度就可实现形状恢复,水蒸汽驱动的形状记忆效应在多个领域都有着潜在的应用价值。本文拟建立一个热-力-化学多场耦合的理论模型来模拟非晶态高聚物的水蒸汽驱动形状记忆行为。该理论模型采用自由体积的概念来模拟玻璃态转变,采用Fick定律来模拟水蒸汽在高聚物基体中的扩散行为。相关有限元模拟结果表明,该模型能定性地描述文献中观察到的恢复温度、相对湿度以及溶剂分子扩散速度对形状恢复行为的影响,也能模拟复杂变形条件下水蒸汽驱动的形状记忆效应。     

水蒸汽驱动高聚物形状记忆效应的力学模拟

部分形状记忆高聚物在相对湿度较高的环境中会从其临时形状恢复到永久形状，这种效应被称之为水蒸汽驱动形状记忆效应。由于不需要升高温度就可实现形状恢复，水蒸汽驱动的形状记忆效应在多个领域都有着潜在的应用价值。本文拟建立一个热-力-化学多场耦合的理论模型来模拟非晶态高聚物的水蒸汽驱动形状记忆行为。该理论模型采用自由体积的概念来模拟玻璃态转变，采用Fick定律来模拟水蒸汽在高聚物基体中的扩散行为。相关有限元模拟结果表明，该模型能定性地描述文献中观察到的恢复温度、相对湿度以及溶剂分子扩散速度对形状恢复行为的影响，也能模拟复杂变形条件下水蒸汽驱动的形状记忆效应。     

Combined deformation- and temperature-induced scission in a rubber cylinder in torsion

When an elastomeric material is deformed and subjected to temperatures above some characteristic value T_cr (near for natural rubber), it undergoes time and temperature dependent chemical changes consisting of scission and crosslinking of its macromolecular structure. The process continues until the temperature decreases below T_cr. Experiments carried out in uniaxial extension have shown that the chemical changes are independent of stretch ratio within moderate stretches. It is reasonable to expect that the chemical changes would be affected by sufficiently large deformations, an interaction referred to as ‘mechanochemistry’. A kinetic theory of the breakdown of solids by Zhurkov [Kinetic concept of strength of solids, Int. J. Fract. Mech. 1 (1965) 311-323. [15]] attributes this interaction to the lowering of activation energy by mechanical work.In a recent constitutive theory, an expression was developed that relates the chemical kinetics of scission of the original elastomeric network to time, temperature and activation energy. The kinetic theory of Zhurkov suggests a method for modifying this expression to account for the influence of deformation. This is explored in the case of simple shear deformations, such as those occurring during torsion of elastomeric cylinders held at fixed length. Using the approach of Penn and Kearsley [The scaling law for finite torsion of elastic cylinders, Trans. Soc. Rheology 20 (1976) 227-238. [16]], it is shown that experiments in torsion can be used to determine the influence of shear deformations on the chemical kinetics of scission.     

Several effects of melt viscosity on the nature ofC p —T data aboveT g for acrylate,methacrylate, and hydrocarbon polymers

Using objective computerized statistical procedures, we have examined high precisionC _p data by DSC reported by Wunderlich and Gaur for a series of alkyl acrylate and methacrylate polymers. Although they claimed the data to be linear inT aboveT _g , our results do not support the linear model. One or two endothermic slope changes are revealed aboveT _g in lowT _f polymers (T _f < 20 °C) and at least one exothermic slope change in highT _f polymers (T _f > 20 °C).T _f is the flow temperature of Ueberreiter. Both the first endotherm and the first exotherm occur near (1.22 ± 0.07)T _g , suggesting aT _ll type phenomenon.T _ll varies as \(1/\bar M_n \) . The first exotherm is associated by us with wetting of the DSC pan by molten polymer on the first heating of particulate highT _f polymers. The rate of wetting, and presumably the magnitude of the exotherm, depends in part on the ratio,γ/η, whereγ is surface tension andη is melt viscosity of the molten polymer. Sinceγ is relatively constant, the molecular weight and temperature dependence for rate of wetting resides inη, which depends on \(\bar M_w \) . For \(\bar M_n > > \bar M_c \) , a second exothermic event caused by sintering, and also controlled by η, may be present. The interactive roles of \(\bar M_n ,\bar M_w ,\bar M_w /\bar M_n \) ;M _c (entanglement molecular weight); particle size, and heating rate onC _p —T behaviour are delineated for the first time. LowT _f hydrocarbon polymers, namely atactic polyalphaolefins,C ₃ ,C ₅ ,C ₆ ; PIB; and dienes, PBD and cis-PI, exhibit single or double endotherms. Other results on highT _f polymers showing exothermic effects, notably PS, PnBMA and polyglycidylmethacrylate are cited.     

An investigation on multilayer shape memory polymers under finite bending through nonlinear thermo-visco-hyperelasticity

This study presents a semi-analytical solution to describe the behavior of shape memory polymers(SMPs) based on the nonlinear thermo-visco-hyperelasticity which originates from the concepts of internal state variables and rational thermodynamics. This method is developed for the finite bending of multilayers in a dual-shape memory effect(SME) cycle. The layer number and layering order are investigated for two different SMPs and a hyperelastic material. In addition to the semi-analytical solution...     

Grain size–inclusion size interaction in metal matrix composites using mechanism-based gradient crystal plasticity

Metal matrix composites (MMCs) comprising nano/microcrystalline matrices and reinforcements exhibit impressive mechanical behaviors derived by exploiting the size effects due to development of geometrically necessary dislocations. In such nanostructured MMCs intricate interactions between the grain size d_g and inclusion size d_i may exist in their overall response, but are difficult to isolate in experiments and are also not accounted for in the size-dependent homogenized models. In this paper, we computationally investigate the grain size–inclusion size interaction in model MMCs architectures wherein the grains and inclusions are explicitly resolved. A mechanism-based slip-gradient crystal plasticity formulation (Han et al., 2005a) is implemented in a finite element framework to model polycrystalline mass as an aggregate of randomly oriented single crystals that host elastic inclusions. The slip gradients that develop across grain boundaries and at inclusion–grain interfaces during deformation result in length-scale dependent responses that depend on both d_g and d_i, for a fixed inclusion volume fraction f. For a given d_i and f, the overall hardening exhibits a nonlinear dependence on grain size for d_g ? d_i indicating that interaction effects become important at those length-scales. Systematic computational simulations on bare polycrystalline and MMC architectures are performed in order to isolate the contributions due to grain size, inclusion size and the interaction thereof. Based on these results, an analytical model developed for the interaction hardening exhibits a Hall–Petch type dependence on these microstructural sizes that can be incorporated into homogenized approaches.     

Free volume dependence of polymer viscosity

The Simha–Somcynsky (S–S) equation of state (eos) was used to compute the free volume parameter, h, from the pressure–volume–temperature (PVT) dependencies of eight molten polymers. The predicted by eos variation of h with T and P was confirmed by the positron annihilation lifetime spectroscopy; good agreement was found for h(P = constant) = h(T) as well as for h(T = constant) = h(P). Capillary shear viscosity (η) data of the same polymers (measured at three temperatures and six pressures up to 700 bars), were plotted as logη vs 1/h, the latter computed for T and P at which η was measured. In previous works, such a plot for solvents and silicone oils resulted in a “master curve” for the liquid, in a wide range of T and P. However, for molten polymers, no superposition of data onto a “master curve” could be found. The superposition could be obtained allowing the characteristic pressure reducing parameter, P*, to vary. The necessity for using a “rheological” characteristic pressure reducing parameter, P*_R = κP*, with κ = 1 to 2.1 indicates that the free volume parameter extracted from the thermodynamic equilibrium data may not fully describe the dynamic behavior. After eliminating possibility of other sources for the deviation, the most likely culprit seems to be the presence of structures in polymer melts at temperatures above the glass transition, T _g. For example, it was observed that for amorphous polymers at T ≅ 1.52T _g the factor κ = 1, and the deviation vanish.     

Boundary layer development on a continuous moving surface with a parallel free stream due to impulsive motion

The development of the momentum and thermal boundary layers over a semi-infinite flat plate has been studied when the external stream as well as the plate are impulsively moved with constant velocities. At the same time the temperature of the wall is suddenly raised from T_∞, the temperature of the surrounding fluid, toT _w and maintained at this temperature. The problem has been formulated in a new system of scaled coordinates such that fort?=0 it reduces to Rayleigh type of equation and fort? → ∞ it reduces to Blasius or Sakiadis type of equation. A new scale of time has been used which reduces the region of integration from an infinite region to a finite region which reduces the computational time considerably. The governing singular parabolic partial differential equations have been solved numerically using an implicit finite difference scheme. For some particular cases, analytical solutions have been obtained. The results show that there is a smooth transition from Rayleigh solution to Blasius or Sakiadis solution as the dimensionless timeξ increases from zero to one. The shear stress at the wall is negative for the friction parameterλ<0.5, positive forλ>0.5 and zero forλ=0.5. The zero shear stress at the wall does not imply separation but corresponds to the parallel flow. The surface heat transfer is strongly dependent on the Prandtl numberPr and increases with it. Also forPr<Pr ₀, the surface heat transfer is enhanced as the friction parameterλ increases, but forPr>Pr ₀ it get reduced.     

Compliance of actin filament networks measured by particle-tracking microrheology and diffusing wave spectroscopy

We monitor the time-dependent shear compliance of a solution of semi-flexible polymers, using diffusing wave spectroscopy (DWS) and video-enhanced single-particle-tracking (SPT) microrheology. These two techniques use the small thermally excited motion of probing microspheres to interrogate the local properties of polymer solutions. The solutions consist of networks of actin filaments which are long semi-flexible polymers. We establish a relationship between the mean square displacement (MSD) of microspheres imbedded in the solution and the time-dependent creep compliance of the solution, <Δr ²(t)>=(k _B T/πa)J(t). Here, J(t) is the creep compliance, <Δr ²(t)> is the mean-square displacement, and a is the radius of the microsphere chosen to be larger than the mesh size of the polymer network. DWS allows us to measure mean square displacements with microsecond temporal resolution and Ångström spatial resolution. At short times, the mean square displacement of a 0.96μm diameter sphere in a concentrated actin solution displays sub-diffusion. <Δr ²(t)>∝t ^{, with a characteristic exponent =0.78±0.05, which reflects the finite rigidity of actin. At long times, the MSD reaches a plateau, with a magnitude that decreases with concentration. The creep compliance is shown to be a weak function of polymer concentration and scales as J _p ∝c –1.2±0.3. This exponent is correctly described by a recent model describing the viscoelasticity of semi-flexible polymer solutions. The DWS and video-enhanced SPT measurements of the compliance plateau agree quantitatively with compliance measured independently using classical mechanical rheometry for a viscous oil and for a solution of flexible polymers. This paper extends the use of DWS and single-particle-tracking to probe the local mechanical properties of polymer networks, shows for the first time the proportionality between mean square displacement and local creep compliance, and therefore presents a new, direct way to extract the viscoelastic properties of polymer systems and complex fluids.}