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At least 19 records

Characterization of Nonlinear Rate Dependent Response of Shape Memory Polymers

Shape Memory Polymers (SMPs) are a class of polymers, which can undergo deformation in a flexible state at elevated temperatures, and when cooled below the glass transition temperature, while retaining their deformed shape, will enter and remain in a rigid state. Upon heating above the glass transition temperature, the shape memory polymer will return to its original, unaltered shape. SMPs have been reported to recover strains of over 400%. It is important to understand the stress and strain recovery behavior of SMPs to better develop constitutive models which predict material behavior. Initial modeling efforts did not account for large deformations beyond 25% strain. However, a model under current development is capable of describing large deformations of the material. This model considers the coexisting active (rubber) and frozen (glass) phases of the polymer, as well as the transitions between the material phases. The constitutive equations at the continuum level are established with internal state variables to describe the microstructural changes associated with the phase transitions. For small deformations, the model reduces to a linear model that agrees with those reported in the literature. Thermomechanical characterization is necessary for the development, calibration, and validation of a constitutive model. The experimental data reported in this paper will assist in model development by providing a better understanding of the stress and strain recovery behavior of the material. This paper presents the testing techniques used to characterize the thermomechanical material properties of a shape memory polymer (SMP) and also presents the resulting data. An innovative visual-photographic apparatus, known as a Vision Image Correlation (VIC) system was used to measure the strain. The details of this technique will also be presented in this paper. A series of tensile tests were performed on specimens such that strain levels of 10, 25, 50, and 100% were applied to the material while it was above its glass transition temperature. After deforming the material to a specified applied strain, the material was then cooled to below the glass transition temperature (Tg) while retaining the deformed shape. Finally, the specimen was heated again to above the transition temperature, and the resulting shape recovery profile was measured. Results show that strain recovery occurs at a nonlinear rate with respect to time. Results also indicate that the ratio of recoverable strain/applied strain increases as the applied strain increases.

Volk, Brent↗

Medical applications of shape memory polymers

Shape memory polymers are described here and major advantages in some applications are identified over other medical materials such as shape memory alloys (SMA). A number of medical applications are anticipated for shape memory polymers. Some simple applications are already utilized in medical world, others are in examination process. Lately, several important applications are being considered for CHEM foams for self-deployable vascular and coronary devices. One of these potential applications, the endovascular treatment of aneurysm was experimentally investigated with encouraging results and is described in this paper as well.

cold hibernated elastic memory (CHEM)↗

Polyurethane Microparticles for Stimuli Response and Reduced Oxidative Degradation in Highly Porous Shape Memory Polymers

Shape memory polymers (SMPs) have been found to be promising biomaterials for a variety of medical applications; however, the clinical translation of such technology is dependent on tailorable properties such as gravimetric changes in degradation environments. For SMPs synthesized from amino-alcohols, oxidation resulting in rapid mass loss may be problematic in terms of loss of material functionality as well as toxicity and cytocompatibility concerns. Control of gravimetric changes was achieved through the incorporation of small molecule antioxidants, either directly into the polymer matrix or included in microparticles to form a SMP composite material. Direct incorporation of small molecule antioxidants, such as phenolic alcohols, was found to alter shape memory attributes and increase elastic modulus at the expense of the strain to failure. Such changes could not ensure retention of the antioxidants and therefore did not increase oxidative stability. However, the inclusion of antioxidants in microparticles was found to produce materials with similar thermomechanical and shape memory properties while increasing oxidative resistance compared to controls. The microparticle composite SMPs also act as a platform for environmental sensing, such as pH-dependent fluorescence shifts and payload release, as demonstrated by fluorescent dyes and the release of antioxidants. The use of polyurethane-urea microparticles in porous SMPs is demonstrated to increase biostability of the materials, by approximately 25%, and ultimately extend their lifespan for use in aneurysm occlusion as determined through calculated in vivo degradation rates corresponding to a porcine aneurysm environment.

Weems, A. C.↗

Volumetric additive manufacturing of shape memory polymers

Shape memory polymers (SMPs) capable of recovering from a deformed state through heating were 3D printed using volumetric additive manufacturing, which enabled the layerless, single-step fabrication of self-standing tripod and actuating gripper structures.

36 MATERIALS SCIENCE↗

Shape memory polymers

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

59 BASIC BIOLOGICAL SCIENCES↗

Shape memory polymers

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

Wilson, Thomas S.↗

AC Electric Field Activated Shape Memory Polymer Composite

Shape memory materials have drawn interest for applications like intelligent medical devices, deployable space structures and morphing structures. Compared to other shape memory materials like shape memory alloys (SMAs) or shape memory ceramics (SMCs), shape memory polymers (SMPs) have high elastic deformation that is amenable to tailored of mechanical properties, have lower density, and are easily processed. However, SMPs have low recovery stress and long response times. A new shape memory thermosetting polymer nanocomposite (LaRC-SMPC) was synthesized with conductive fillers to enhance its thermo-mechanical characteristics. A new composition of shape memory thermosetting polymer nanocomposite (LaRC-SMPC) was synthesized with conductive functionalized graphene sheets (FGS) to enhance its thermo-mechanical characteristics. The elastic modulus of LaRC-SMPC is approximately 2.7 GPa at room temperature and 4.3 MPa above its glass transition temperature. Conductive FGSs-doped LaRC-SMPC exhibited higher conductivity compared to pristine LaRC SMP. Applying an electric field at between 0.1 Hz and 1 kHz induced faster heating to activate the LaRC-SMPC s shape memory effect relative to applying DC electric field or AC electric field at frequencies exceeding1 kHz.

Kang, Jin Ho↗

Design, characterization and shape recovery behavior of 3D/4D printed shape memory polymers (SMPs)

Shape memory polymers (SMPs) represent a paradigm shift in material science, uniquely capable of undergoing reversible shape transformations triggered by external stimuli, positioning them as pivotal in developing next-generation biomedical devices, aerospace components, and adaptive structures. Extensive research has been done on SMPs with a major focus on high-temperature programming methods, which can limit energy efficiency and applicability with temperature-sensitive materials. Additionally, while various SMP blends have demonstrated great potential, limited work has been done on the suitability for 3D printing these materials, particularly under high-strain and ambient temperature programming conditions. In this study, a three-component optimized SMP composition was evaluated by 3D printing via the Material Extrusion (MEX) technique and investigating its ambient temperature-programming behavior at high strains. The SMP formulation studied was a tailored blend of thermoplastic polyurethane (TPU), polycaprolactone (PCL), and an octadecane diol-based copolymer (OBC) that exhibits robust shape memory behavior, high strain tolerance, and efficient force generation. Rigorous thermal, mechanical, and shape recovery analyses, along with optimized printing parameters and consistent shape recovery rates of up to 90%, were achieved under dynamic mechanical analysis (DMA), even under ambient programming conditions. This work demonstrates the SMP composition’s potential for adaptive, self-deployable systems with 4D printing characteristics ideal for bio-inspired structures and artificial muscle fibers.

Sudan, Kavish [University of Louisville, KY]↗

High Energy Density Shape Memory Polymers Using Strain-Induced Supramolecular Nanostructures

Shape memory polymers are promising materials in many emerging applications due to their large extensibility and excellent shape recovery. However, practical application of these polymers is limited by their poor energy densities (up to ~1 MJ/m 3 ). Here, we report an approach to achieve a high energy density, one-way shape memory polymer based on the formation of strain-induced supramolecular nanostructures. As polymer chains align during strain, strong directional dynamic bonds form, creating stable supramolecular nanostructures and trapping stretched chains in a highly elongated state. Upon heating, the dynamic bonds break, and stretched chains contract to their initial disordered state. This mechanism stores large amounts of entropic energy (as high as 19.6 MJ/m 3 or 17.9 J/g), almost six times higher than the best previously reported shape memory polymers while maintaining near 100% shape recovery and fixity. The reported phenomenon of strain-induced supramolecular structures offers a new approach toward achieving high energy density shape memory polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Processable, tunable thiol-ene crosslinked polyurethane shape memory polymers

An embodiment includes a platform shape memory polymer system. Such an embodiment exhibits a blend of tunable, high performance mechanical attributes in combination with advanced processing capabilities and good biocompatibility. A post-polymerization crosslinking synthetic approach is employed that combines polyurethane and thiol-ene synthetic processes. Other embodiments are described herein.

Hearon, Keith↗

Electric Field Activated Shape Memory Polymer Composite

Provided is an electrically activated shape memory polymer composite capable of thermal shape reformation using electric power to heat the composite through its matrix glass transition temperature. The composite includes an adaptable polymer matrix component using a diglycidyl ether resin, at least one substantially well-dispersed conductive or magnetic nano-filler component, and at least one elastic, laminated layer. Also provided are methods of preparing the composite and methods of activating the composite. A shape reformation of the composite is triggered by applying an electric field at DC and/or at a frequency above about 1.mu.Hz for a sufficient time.

Kang, Jin Ho↗

Solvent depression of transition temperature to selectively stimulate actuation of shape memory polymer foams

An embodiment of the invention is a shape memory polymer (SMP) foam designed to recover its original shape through exposure to a solvent. Thermo-responsive SMPs are polymers designed to maintain a programmed secondary shape until heated above their transition temperature, upon which the polymer recovers its original, or primary, shape. The thermo-responsive SMP foam is programmed to its secondary shape prior to use, typically compression of the foam to a small volume, and remains in this programmed shape until exposed to a selected solvent such as dimethyl sulfoxide or ethyl alcohol. Upon exposure to the solvent, the transition temperature of the SMP foam decreases below the temperature of the environment and the SMP foam actuates to its primary shape. The SMP foam is tailored to actuate upon exposure to specific solvents while minimizing or preventing actuation when exposed to water or other solvents. This selective solvent actuation can be used to increase working time of a SMP foam device, that is, the time allowed for use of a device without undesired actuation, while maintaining functional SMP actuation. Solvent actuated SMP foams can be used in various applications including, but not limited to, treatment of aneurysms and arterio-venous malformations, tissue engineering, and wound healing.

Boyle, Anthony↗

Methods of Making and Using Shape Memory Polymer Composite Patches

A method of repairing a composite component having a damaged area including: laying a composite patch over the damaged area: activating the shape memory polymer resin to easily and quickly mold said patch to said damaged area; deactivating said shape memory polymer so that said composite patch retains the molded shape; and bonding said composite patch to said damaged part.

Hood, Patrick J.↗

Shape-memory polymer foam device for treating aneurysms

A system for treating an aneurysm in a blood vessel or vein, wherein the aneurysm has a dome, an interior, and a neck. The system includes a shape memory polymer foam in the interior of the aneurysm between the dome and the neck. The shape memory polymer foam has pores that include a first multiplicity of pores having a first pore size and a second multiplicity of pores having a second pore size. The second pore size is larger than said first pore size. The first multiplicity of pores are located in the neck of the aneurysm. The second multiplicity of pores are located in the dome of the aneurysm.

Ortega, Jason M.↗

Post polymerization cure shape memory polymers

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Wilson, Thomas S.↗

Post polymerization cure shape memory polymers

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Wilson, Thomas S.↗

A Study of Shape Memory Polymer Based Slat-Cove Filler

Aircraft noise reduction is an application of current intense interest for which smart materials show significant potential. Specifically, the aeroacoustic noise produced by the unsteady aerodynamic flow about the leading-edge high-lift device, such as leading-edge slat, of typical transport-aircraft wings is of particular interest. Concepts with the most promise to mitigate this noise source, most notably the slat-cove filler concept, have focused on highly reconfigurable structures that change shape between different phases of the flight envelope. These shape changes often involve large deformation, which has stimulated the consideration of shape memory materials. In recent years, shape memory materials (SMMs) have drawn greater interest for applications such as smart fabrics, intelligent medical devices, self-deployable space structures, morphing structures and packaging. Compared to other shape memory materials, like shape memory alloys (SMAs) or shape memory ceramics (SMCs), shape memory polymers (SMPs) have desirable advantages such as high elastic deformation to enable large shape change, broad tailorability of mechanical properties, potential biocompatibility and biodegradability, ductility, light weight and ease of processing. However, SMPs still have some critical disadvantages such as insufficient mechanical and thermal characteristics for structural applications, low recovery stress, and long response time. The new LaRC shape memory thermosetting polymer composite (LaRC-SMPC) discussed herein was synthesized with nontoxic monomers and conductive/magnetic fillers to yield enhanced thermal/mechanical characteristics and faster response times. LaRC-SMPCs with a variety of fiber reinforcements [Kevlar®, carbon fiber (standard and thin-ply), and carbon-nanotube (CNT) sheet] were fabricated to tailor the physical properties and test for suitability as a slat-cove filler (SCF). The performance of SCF prototypes fabricated with the developed LaRC-SMPCs was evaluated using a bench-top test apparatus. The SCFs made of Kevlar® fiber fabric or carbon fiber fabric infused shape memory polymer composite (SMPC) exhibited kinking during simulated deployment and stowage, which can be problematic during operation. The SCF made of CNT sheet/SMP composite did not exhibit kinking, but the deployment was sluggish compared to carbon fiber fabric/SMP composite. This report documents the evolution of designing SMPCs as slat-cove fillers for aircraft noise reduction. In the course of the investigation, several 2 approaches were investigated to address shortcomings in material characteristics based on performance requirements of operational slat-cove fillers.

Kang, Jin Ho↗

High-Temperature Shape Memory Polymers

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Yoonessi, Mitra↗