Effects of thermal rates on the thermomechanical behaviors of amorphous shape memory polymers

Shape memory polymers (SMPs) are polymers that can recover a large pre-deformed shape in response to environmental stimuli, such as temperature, light, etc. For a thermally triggered (or activated) amorphous SMP, the pre-deformation and recovery of the shape require the temperature of the material to traverse the glass transition temperature T _g under constrained or free conditions. In this paper, effects of thermal rates on the thermomechanical behaviors of amorphous SMPs are investigated. Under uniaxial compression, during a temperature cycle (cooling followed by heating), the stress decreases to zero as the temperature decreases to below the glass transition temperature, and increases to a value larger than the initial stress (termed stress overshoot) as the temperature is raised above the glass transition temperature. These observations are examined by a thermoviscoelasticity model that couples the nonequilibrium structural relaxation and temperature dependent viscoelastic behavior of the material. In addition, using this model, stress-temperature behaviors during temperature cycles with various thermal rate conditions and tensile loading conditions are studied.     

A thermomechanical constitutive model for an epoxy based shape memory polymer and its parameter identifications

This paper presents a three-dimensional (3D) finite deformation thermomechanical model to study the glass transition and shape memory behaviors of an epoxy based shape memory polymer (SMP) (Veriflex E) and a systematic material parameter identification scheme from a set of experiments. The model was described by viscoelastic elements placed in parallel to represent different active relaxation mechanisms around glass transition temperature in the polymer. A set of standard material tests was proposed and conducted to identify the model parameter values, which consequently enable the model to reproduce the experimentally observed shape memory (SM) behaviors. The parameter identification procedure proposed in this paper can be used as an effective tool to assist the construction and application of such 3D multi-branch model for general SMP materials.     

Shape memory property of microcrystalline cellulose–poly(ε-caprolactone) polymer network with broad transition temperature

Preparation of shape memory polymers (SMPs) with broad transition temperature was an effective method to realize multishape memory effect. In this study, a novel SMP with a broad glass transition temperature (T _g) based on microcrystalline cellulose was prepared. The structure of the SMP was analyzed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance, which can prove the successful synthesis of the material. The thermal properties were investigated with differential scanning calorimetry and dynamic mechanical analysis (DMA). The dual- and multishape memory effects were also quantificationally analyzed by DMA. Further, the influence of programming temperature within T _g on dual-shape memory effect was investigated, and a 1D model was built to explain their relationship.     

Mechanical and radiographic properties of a shape memory polymer composite for intracranial aneurysm coils

An intracranial aneurysm can be a serious condition that can go undetected until the aneurysm ruptures, causing hemorrhaging within the subarachnoid space surrounding the brain. The typical treatment for large aneurysms is by embolization using platinum coils. However, in about 15% of the cases treated by platinum coils, the aneurysm eventually re-opens as a result of the bio-inertness of platinum. One solution to this is to develop suitable materials with increased bio-activity to use as coil implants. In this research, a shape memory polymer (SMP), Calomer™, produced by The Polymer Technology Group, Inc., was investigated as a candidate for aneurysm coils. The SMP was tested to determine its thermo-mechanical properties and the strength of the shape recovery force. Composite SMP specimens containing tantalum filler were produced and tested to determine the mechanical effect of adding this radio-opaque metal. Thermo-mechanical testing showed that the material exhibited a shape recovery force a few degrees above the glass transition temperature, T_g. The effects of the addition were small and included a decrease in T_g and recovery force. SMP coils deployed inside a simulated aneurysm model demonstrate that typical hemodynamic forces do not hinder the shape recovery process. The radio-opacity of the Ta-filled material was characterized with clinical fluoroscopy.     

Analysis and design of smart mandrels using shape memory polymers

Based on the thermomechanical mechanism of shape memory polymers (SMPs), the three-dimensional thermomechanical constitutive equation that can be used in the ABAQUS finite element simulation was derived. Then this paper compiled UMAT subroutine and simulated the thermomechanical behaviors of SMP smart mandrels. In addition, the properties of shape fixity and shape recovery ratio of SMP were considered in detail. Finally, filament winding experiments were proceeded on bottle-shaped and air duct-shaped mandrels and the simple and efficient demoulding of SMP mandrels were verified. The results showed the feasibility of SMP as the smart mandrels from practical application in the future.     

A review of shape memory polymer composites and blends

Shape memory polymers (SMPs) are a kind of very important smart polymers. In order to improve the properties or obtain new functions of SMPs, SMP composites and blends are prepared. We thoroughly examine the research in SMP composites and blends achieved by numerous research groups around the world. The preparation of SMPs composites and blends is mainly for five aims: (1) to improve shape recovery stress and mechanical properties; (2) to decrease shape recovery induction time by increasing thermal conductivity; (3) to create new polymer/polymer blends with shape-memory effect (SME); (4) to tune switch temperature, mechanical properties, and biomedical properties of SMPs; (5) to fabricate shape memory materials sensitive to electricity, magnetic, light and moisture. The trend of SMP composite development is discussed. SMP composites and blends exhibit novel properties that are different from the conventional SMPs and thus can be utilized in various applications.     

Unique Shape Memory Elastomer Associated with Reversible Sacrificial Hydrogen Bonds: Tough and Flexible When below Its Tg

Thermally induced shape memory polymers (SMPs) are fragile and brittle when cooling to a low temperature to generate temporary shapes. In the present study, the authors implement a new design strategy for fabricating elastomeric SMPs with low‐temperature flexibility by engineering reversible sacrificial hydrogen bonds into a chemically crosslinked network. Compatible, amorphous, hindered phenol moieties (Irganox 1010) are incorporated into epoxidized natural rubber (ENR) and the ENR composites are cured with zinc diacrylate (ZDA). Such reversible sacrificial bonds can rupture prior to the rupture of the bonds of the crosslinked network during stretching, which will dissipate energy and facilitate reorientation of the rubber chains. Based on the functional mechanisms, ENR composites exhibit unusual toughness and flexibility and can undergo large deformations even when below their T_g. Irganox 1010 can also be used to tune the glass transition temperature (T_g) and improve the chain mobility of the elastomer sample by providing sufficient intermolecular hydrogen bonding interactions. ENR composites demonstrate thermally triggered shape memory performance. Moreover, the dissociation/reformation of hydrogen bonds upon stretching/cooling can endow the elastomer sample with unique reversible plastics shape memory (RPSM) performance. These SMPs possess excellent shape fixity and recovery.

     

Self-assembled multi-layered carbon nanofiber nanopaper for significantly improving electrical actuation of shape memory polymer nanocomposite

This study presents an effective approach to significantly improve the electrical properties of shape memory polymer (SMP) nanocomposites that show Joule heating triggered shape recovery. Carbon nanofibers (CNFs) were self-assembled to form multi-layered nanopaper to enhance the bonding and shape recovery behavior of SMP, respectively. It was found that both glass transition temperature (Tg) and electrical properties of the SMP nanocomposites have been improved by incorporating multi-layers of self-assembled nanopapers. The electrically actuated shape recovery behavior and the temperature profile during the actuation were monitored and characterized at a voltage of 30 V.     

Effects of initial structure on the shape memory properties of Ti50Ni25Cu25 ribbons

The effect of annealing temperature and initial structure (amorphous and fully crystallized) on shape memory properties of Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbons was studied by using DSC and thermomechanical analyzer (TMA). M_s of the annealed ribbons increased with the annealing temperature below 550 °C. It decreased with annealing temperature above 550 °C. The fully crystallized as-spun ribbon showed the highest shape recovery strain under 45 MPa. With the increase of annealing temperature the recovery strain of the two ribbons decreased significantly.     

Chemical and thermomechanical tailoring of the shape memory effect in poly(ε-caprolactone)-based systems

The thermally activated shape memory response of polymeric materials results from a combination of the material molecular architecture with the thermal/deformational history, or ‘programming’. In this work, we investigate the shape memory response of systems based on poly(ε-caprolactone) (PCL) so as to explore the adoption of proper chemical and thermomechanical tailoring routes. Cross-linked semicrystalline PCL-based materials are prepared by different molecular architectures starting from linear, three- and four-arms star PCL functionalized with methacrylate end groups, allowing to tune the melting temperature, T _m, ranging between 36 and 55 °C. The materials’ ability to display the shape memory is investigated by the application of proper thermomechanical cycles on specimens deformed at two different temperatures (23 and 65 °C, i.e. below and above the T _m, respectively). The shape memory response is studied under dynamic thermal conditions in thermally activated recovery tests, to identify the typical transformation temperatures, and under isothermal conditions at given recovery temperatures, to monitor shape recovery as a function of time. All the specimens are capable of full recovery on specific thermal ranges influenced by both melting and deformation temperatures. Specimens deformed above T _m are able to recover the whole deformation in a very narrow temperature region close to T _m, while those deformed at room temperature display broader recovery processes, those onset at about 30 °C. Isothermal tests reveal that when the deformed material is subjected to a constant recovery temperature, the amount of recovered strain and the time required strongly depend on the particular combination of melting temperature, deformation temperature and recovery temperature.     

Functional Fatigue of Shape Memory Polymers

In the present study the functional fatigue in the commercial SMP Veriflex® which is associated with repeating up to 20 programming/1‐WE cycles has been examined. The material is characterized by a glass temperature T_g of 67 °C, above which it looses all its strength. During tensile testing at 21 °C (T < T_g), stresses steadily increase to 26 MPa as strains approach the rupture strain of 7.6 %. At 80 °C (T > T_g) the material can be strained up to 225 % before rupture occurs while stresses slowly increase to values as low as 0.4 MPa. Thermomechanical cycles including programming, cooling and unloading and heating to trigger the one way effect result in an increase of irreversible strain associated with a corresponding decrease of recovery ratio at the beginning of thermomechanical cycling. In parallel a wavy surface structure evolves during cycling.     

Damage characterization in non-isothermal stretching of acrylics. Part II: Experimental validation

Influence of temperature and strain rate on damage accumulation and large deformation behavior of acrylics was investigated under conditions similar to actual polymer processing. Poly(methyl methacrylate) (PMMA) samples were stretched to large strains at different rates under transient thermal conditions. During testing, specimens were cooled down from temperatures above glass transition temperature (θ_g) to temperatures well-below θ_g inducing a transition from rubbery state to solid state. Contrary to common practice of studying thermo-mechanical coupling in terms of adiabatic heating; in proposed experimental study, temperature effect on mechanical response of material was emphasized by externally intervening temperature variation within specimen. An improved version of dual-mechanism constitutive model presented in Part I [Gunel, E.M., Basaran, C., 2010. Damage characterization in non-isothermal stretching of acrylics. Part I: Theory. Mechanics of Materials] was proposed to predict thermo-mechanical response of amorphous polymer below and above θ_g. Applicability of proposed constitutive model for the specific case of non-isothermal stretching of PMMA at different test conditions was demonstrated by incorporating it into a finite element scheme. Constitutive model was reasonably accurate to capture observed temperature-displacement-force history in experimental study. Damage evolution under different testing conditions was studied in terms of irreversible thermal and mechanical entropy production.     

热致形状记忆聚合物的热力学性能

形状记忆聚合物作为一类新型功能材料,具有独特优点,近年来在机理研究和工程应用方面均受到高度重视。由于其功能实现主要是通过热激励实现的,建立其热力学本构方程是开展该类功能材料变形机理研究的基础。本文首先通过单拉伸实验研究了热致形状记忆聚氨酯在预应变分别为0%、5%、10%和20%下的形状冻结和恢复性能。考虑其冻结/恢复时间延迟效应、应力松弛效应以及热变形效应的影响,对其变形过程进行了理论分析。结果证实,理论预测值与实验测试结果较为吻合。     

4D Printing-Encapsulated Polycaprolactone–Thermoplastic Polyurethane with High Shape Memory Performances

There are a few shape memory polymers (SMPs) like polylactic acid (PLA) and polyurethane (PU) that are 4D printable, and other SMPs must be synthesized with a complicated chemical lab effort. Herein, considering dual-material extrusion printing and microscopic mechanism behind shape memory effect (SME), bilayer-encapsulated polycaprolactone (PCL)–thermoplastic polyurethane (TPU) shape memory composite structures are 4D printed for the first time. The SME performance is investigated by assessing fixity, shape recovery, stress recovery, and stress relaxation under bending and compression loading modes. PCL, TPU, and melting temperature of PCL play the role of switching phase, net point, and transition temperature, respectively. Due to the destruction and dripping of molten PCL in contact with water, PCL is encapsulated by TPU. Encapsulation successfully solves the challenge of bonding/interface between printed layers, and the results show that the SME performance of the encapsulated structures is higher than bilayer PCL–TPU one's. Experiments reveal that maximum stress recovery in 4D-printed composites remains constant over time. This is a great achievement compared to the previous extrusion-based SMP structures that have great weakness in stress relaxation due to weak and low crystalline fractions and the unraveling of molecular entanglements in semicrystalline and amorphous thermoplastic SMPs, respectively.     

Strain rate- and temperature-dependent tensile properties of an epoxy-based, thermosetting, shape memory polymer (Veriflex-E)

In this study, the inelastic deformation behavior of an epoxy-based, thermally triggered shape memory polymer resin, known as Veriflex-E, was investigated. The experimental program was designed to explore the influence of strain rate on monotonic loading at various temperatures which is needed to establish the design space of SMPs in load bearing applications. Thermally actuated shape memory polymers can be thought of as having two phases separated by the glass transition temperature (T _g ). At temperatures below the T _g , Veriflex-E exhibits a high elastic modulus and positive, non-linear strain rate sensitivity in monotonic loading. The Poisson’s ratio at room temperature is independent of the strain rate, but dependent upon the strain magnitude. As the temperature is increased, the strain rate sensitivity in monotonic loading decreases. Well above the T _g , the elastic modulus drops by several orders of magnitude. In this high temperature region, the material achieves strain levels well above 100% and Poisson’s ratio is constant at 0.5 regardless of strain rate or strain magnitude.     

Significantly improving infrared light-induced shape recovery behavior of shape memory polymeric nanocomposite via a synergistic effect of carbon nanotube and boron nitride

The present work studies the thermomechanical properties and infrared light-induced shape memory effect (SME) in shape memory polymer (SMP) nanocomposite incorporated with carbon nanotube (CNT) and boron nitride. The combination of CNT and boron nitride results in higher glass transition temperature, mechanical strength and thermomechanical strength. While CNTs are employed to improve the absorption of infrared light and thermally conductive property of SMP, boron nitrides facilitate heat transfer from CNTs to the polymer matrix and thus to enable fast response. A unique synergistic effect of CNT and boron nitride was explored to facilitate the heat transfer and accelerate the infrared light-induced shape recovery behavior of the shape memory polymeric nanocomposite.     

Thermo/moisture responsive shape-memory polymer for possible surgery/operation inside living cells in future

The recoverable strain of shape-memory polymers (SMPs) is an order higher than their metal counterpart, i.e., shape-memory alloys. The recent finding of the influence of moisture on the glass transition temperature of a polyurethane SMP, which is traditionally known for its thermo-responsive nature, enables us to realize not only water-driven for shape recovery, but also recovery following a pre-determined sequence. Utilizing these features of this SMP, we propose the concept of delivering a tiny device which is made of this material into a pore through a very small hole. The feasibility of the concept is demonstrated experimentally. This concept could eventually be used to deliver a micro/nano device into living cells for surgery or operation inside of them.     

Preparation and mechanism of shape memory bismaleimide resins with high transition temperature,high toughness and good processability

Developing shape memory polymers (SMPs) with high transition temperature (T_trans), good toughness and good processability (low molding temperature and solvent-free) is still a great challenge. Herein, a new type of thermosetting shape memory resin (BDPH) is developed based on bismaleimide resin (BD), cardo-polyetherketone (PEK-C) and multi-maleimide-terminated branched polysiloxane (HSi). The effect and mechanism of the compositions on structure and key properties (heat resistance, toughness and shape memory effect) of resins were systematically investigated. Results show that BDPH system has outstanding integrated properties. Specifically, for the resin with optimal composition (BDPH10), its T_trans is as high as 292 °C, about 30 °C higher than that of thermosetting SMPs (TS-SMPs) reported so far; meanwhile, the maximum curing temperature of BDPH10 is about 40 °C lower than those of TS-SMPs of which T_trans values are higher than 270 °C. The shape fixed rate and shape recovery rate of BDPH10 are 97.5 and 98.7%, respectively; besides, BDPH10 has high toughness, its impact strength is 21.8 kJ m^?2, about two times of that of BD resin, overcoming the drawback of traditional thermosetting SMPs. The mechanism behind those attractive performances of BDPH is proved to be attributed to the effects derived from PEK-C and HSi.     

Experimental characterization and thermoviscoelastic modeling of strain and stress recoveries of an amorphous polymer network

An acrylate polymer network was submitted to thermomechanical shape memory cycles. The set of experiments characterized the material stress-free strain recovery and the strain-constrained stress recovery in uniaxial tension. Experimental parameters like temperature of strain fixation, amount of strain and heating rate, were varied in order to provide a relatively complete set of experimental data. A model combining the amorphous polymer viscoelasticity and its time–temperature superposition property was used to predict the shape memory behavior of the acrylate polymer network. All the model parameters were characterized using classical tests for mechanical characterization of polymers, which do not include shape memory tests. Model predictions obtained by finite element simulations compared very well to the experimental data and therefore the model relevance for computer assisted application design was assessed.     

Layered Titanium Carbide-Mediated Fast Shape Switching and Excellent Thermal and Electrical Transport in Shape-Memory-Polymer Composites for Smart Technologies: MAX Versus MXene

Stimuli-responsive materials can frequently tune between their temporary and original shapes, and have the potential for artificial intelligence-based technologies in robotics, aerospace, biomedical, engineering, security, etc. Shape memory polymers (SMPs) are promising for these technologies but their inadequate thermal and electrical characteristics causing slow shape recovery limit their practical applications. Herein, for the first time, comprehensively and precisely the shape memory polyurethane (PU), a promising SMP, via a variety of novel layered titanium carbides fillers, namely, Ti₂AlC (MAX₁), Ti₃AlC₂ (MAX₂), and Ti₃C₂ (MXene), is engineered. The resultant PU-composites show 30–50% faster shape recovery in different environments, 20–25% greater extent of shape recovery in the load-constrained environment, 100–125% higher thermal conductivity, and 700–16 000× higher electrical current. Importantly, the reinforcement of even a small amount of MAX and MXene (such as 0.25 wt%) has largely boosted the performance of PU. Considering ease of processability and performance enhancement factors, the MAX-phase fillers may be preferred over MXene-phase fillers for next-generation composites development. Employing PU composite component as both heat-sensor and actuator, a unique heat detector/fire alarm device that works successfully in simulated heat and fire environments is demonstrated. This work is crucial for enabling futuristic technologies.