Significantly improving electro‐activated shape recovery performance of shape memory nanocomposite by self‐assembled carbon nanofiber and hexagonal boron nitride

This study presents two effective approaches to significantly improve the electro‐thermal properties and electro‐activated shape recovery performance of shape memory polymer (SMP) nanocomposites that are incorporated with carbon nanofibers (CNFs) and hexagonal boron nitrides (h‐BNs), and show Joule heating triggered shape recovery. CNFs were self‐assembled and deposited into buckypaper form to significantly improve the electrical properties of SMP and achieve the shape memory effect induced by electricity. The h‐BNs were either blended into or self‐assembled onto CNF buckypaper to significantly improve the thermally conductive properties and electro‐thermal performance of SMPs. Furthermore, the shape recovery behavior and temperature profile during the electrical actuation of the SMP nanocomposites were monitored and characterized. It was found that a unique synergistic effect of CNFs and h‐BNs was presented to facilitate the heat transfer and accelerate the electro‐activated shape recovery behavior of the SMP nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40506.     

Thermomechanical and shape memory properties of thermosetting shape memory polymer under compressive loadings

Shape memory polymers (SMPs) are an emerging class of active polymers that may be used for a range of reconfigurable structures. In this study, the thermomechanical and shape memory behavior of a thermosetting SMP was investigated using large‐scale compressive tests and small‐scale indentation tests. Results show that the SMP exhibits different deformation modes and mechanical properties in compression than in tension. In glassy state, the SMP displays significant plastic deformation and has a much higher modulus and yield strength in comparison to those obtained in tension. In rubbery state, the SMP behaves like a hyperelastic material and again has a much higher modulus than that obtained in tension. The SMPs were further conditioned separately in simulated service environments relevant to Air Force missions, namely, (1) exposure to UV radiation, (2) immersion in jet‐oil, and (3) immersion in water. The thermomechanical and shape recovery properties of the original and conditioned SMPs were examined under compression. Results show that all the conditioned SMPs exhibit a decrease in T_g as compared to the original SMP. Environmental conditionings generally result in higher moduli and yield strength of the SMPs in the glassy state but lower modulus in the rubbery state. In particular, the UV exposure and water immersion, also weaken the shape recovery abilities of the SMPs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A simulation method to analyze chemo‐mechanical behavior of swelling‐induced shape‐memory polymer in response to solvent

A network of thermally responsive shape‐memory polymers (SMPs) could imbibe a quantity of solvent molecules to swell, and subsequently induces a chemical potential change in polymer. When an equilibrium is reached between the mechanical load and the chemical potential of polymer network and solvent, the SMP polymer usually swells with a field of inhomogeneous and anisotropic deformation, which is considered to be equivalent to a hyperelastic field. We implement this theory in the free‐energy function equation, and analyze examples of swelling‐induced deformation and shape recovery behavior. This work may provide a powerful tool to study complex swelling‐induced shape‐memory behavior of SMPs in response to the immersing solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Porous inorganic-organic shape memory polymers

Thermoresponsive shape memory polymers (SMPs) are a type of stimuli-sensitive materials that switch from a temporary shape back to their permanent shape upon exposure to heat. While the majority of SMPs have been fabricated in the solid form, porous SMP foams exhibit distinct properties and are better suited for certain applications, including some in the biomedical field. Like solid SMPs, SMP foams have been restricted to a limited group of organic polymer systems. In this study, we prepared inorganic-organic SMP foams based on the photochemical cure of a macromer comprised of inorganic polydimethylsiloxane (PDMS) segments and organic poly(ε-caprolactone) (PCL) segments, diacrylated PCL(40)-block-PDMS(37)-block-PCL(40). To achieve tunable pore size with high interconnectivity, the SMP foams were prepared via a refined solvent-casting/particulate-leaching (SCPL) method. By varying design parameters such as degree of salt fusion, macromer concentration in the solvent and salt particle size, the SMP foams with excellent shape memory behavior and tunable pore size, pore morphology, and modulus were obtained.     

State diagram of phase transition temperatures and solvent‐induced recovery behavior of shape‐memory polymer

In this study we analyzed the phase and state transitions of shape‐memory polymers (SMPs)/solvent mixtures using the Flory–Huggins (FH) theory by extension of Vrentas and the Couchman–Karasz theory for glass transition, as well as Clausius–Clapeyron relation for melting transition. Using scaling relations of model parameters, we have obtained a theoretical prediction of state diagrams of the phase transition temperature and solvent‐induced recovery in SMPs. The inductive decrease in transition temperature is identified as the driving force for the solvent‐induced shape‐memory effect in SMPs Consequently, the thermodynamics of the polymer solution and the relaxation theory were employed to characterize the dependencies of shape recovery time on the FH parameter and the ratio of the molar volume of solute to solvent. With the estimated model parameters, we constructed the state diagram for SMP, which provides a powerful tool for design and analysis of phase transition temperatures and solvent‐induced recovery. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication of a functionally graded and magnetically responsive shape memory polymer using a 3D printing technique and its characterization

In this study, a three‐dimensional printing technique is applied for the fabrication of novel functionally graded magnetic shape memory polymers (SMPs) to create high‐resolution multimaterial shape memory architectures. This approach is applied to a copolymer network of photocurable methacrylate using high projection stereolithography. Carbonyl iron particles (CIPs) were physically embedded in a polymer matrix to add magnetic functions to the SMPs. The glass transition characteristics and shape memory effect were also investigated by varying the composition of the SMP. The microstructured, lightweight SMPs showed interesting shape memory behaviors, as observed in hot environment. The almost perfect strain recovery rate of poly(ethylene glycol) dimethacrylate was measured (99.95% using a tension set bar). The results of dynamic mechanical analysis and thermogravimetric analysis reveal an increment in the thermal conductivity after embedding the CIPs. Further, the results of dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy reveal close interaction between the particles and matrix. X‐ray diffraction was used to characterize the iron particles and polymer structure. These results, along with the electrical and magnetic tests, strongly support the remote controllability of the material properties of the present functionally graded magnetic SMPs for a broad range of temperature and/or magnetically responsive material applications by using eddy current heating and/or magnetorheological polymeric effects. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45997.     

Numerical study of smart honeycomb core using shape memory polymers

Shape memory polymers (SMPs) attract widespread attention because they are able to maintain a temporary deformation after unloading and recover the initial shape under high temperature conditions. Based on a three‐dimensionally constitutive equation of SMPs, a finite element program is followed by compiling user‐defined material subroutine, which describes the shape memory behavior of thermo‐mechanical experiment. A honeycomb core using SMP is designed, which has the ability to recover the initial shape after deformation and be used as a smart core for sandwich structures. To prove their advantages in the engineering application, a series of thermodynamic behaviors of the SMP honeycomb core are simulated, including loading at high temperature, cooling, unloading at the low temperature, and recovering original shape on heating. Shape memory behaviors of tensile, compressive, bending, and locally sunken deformations are demonstrated and the effect of time and temperature on the recovery process is discussed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45672.     

Hybrid Electroactive Shape Memory Polymer Composites with Room Temperature Deformability

Polymeric blend shape memory polymers (SMPs) can be constructed from two immiscible polymeric matrices. The shape recovery behavior of these composite systems can be easily controlled by varying the ratio of the polymer blends. It has been recently discovered that the functionality of SMPs can be further enhanced with electroactive ability through the use of conductive fillers. However, the fillers may negatively interact with the SMPs and cause a reduction in the elongation at failure thereby diminishing the shape recovery performance. It is proposed that a plasticizer can be utilized to alter the microstructure of the SMPs with conductive fillers. In this study, a new hybrid SMP is developed by combining single‐walled carbon nanotubes (SWCNT) into a poly(lactic acid) (PLA) and thermoplastic polyurethane (TPU) SMP system containing poly(ethylene glycol) (PEG) plasticizer. The incorporation of PEG is able to lower the activation temperature, while enhancing dispersion of SWCNT. The presence of SWCNT can stabilize the SMP system and significantly enhance the shape‐fixing capability after deformation at room temperature conditions. By carefully controlling the formulation, an electroactive SMP can be created by optimizing the amount of SWCNT and PEG plasticizer.     

Reconfiguration and shape memory triggered by heat and light of carbon nanotube–polyurethane vitrimer composites

Thermoset shape‐memory polymers (SMPs) are widely applied because of their superiority in maintaining permanent shapes. However, the inferiority of this material is also conspicuous, namely the loss of reprocessing ability owing to the chemically crosslinked structure. Fortunately, a new class of SMPs, known as “vitrimers,” was discovered, which can be reshaped or reprocessed via topological rearrangement due to the existence of dynamic covalent bonds. Thus, this new thermoset SMP could become a novel solution. In this paper, carbon nanotube–polyurethane vitrimer (CNT‐PUV) composites have been prepared, which possess the capability of thermally induced shape memory based on entropy changes and thermal reconfiguration based on transcarbamoylation reactions of carbamate bonds. In addition, the introduction of CNTs endows them with properties of near‐infrared (NIR) triggered shape memory and reconfiguration due to the photothermal conversion effect of CNTs. Besides, due to the character of the NIR laser, step‐by‐step shape recovery of CNT‐PUVs is realized from predefined temporary shapes to a permanent shape. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45784.     

Effect of the crosslinking density and programming temperature on the shape fixity and shape recovery in epoxy–anhydride shape‐memory polymers

In addition to the fabrication of thermoset epoxy–anhydride shape‐memory polymers (SMPs), a systematic experimental investigation was conducted to characterize the crosslinking density, micromorphology, thermal properties, mechanical properties, and shape‐memory effects in the epoxy SMP system, with a focus on the influence of the crosslinking density and programming temperature on the shape‐fixity and shape‐recovery behaviors of the polymers. On the basis of the crosslinking density information determined by NMR technology, we concluded that the effect of the crosslinking density on the shape‐fixity behaviors was dependent on the programming temperature. The advantage of a nice combination of crosslinking density and programming temperature provided an effective approach to tailor the actual shape recovery within a wide range. The increasing crosslinking density significantly improved the shape‐recovery ratio, which could be further improved through a decrease in the programming, whereas the crosslinking density was more fundamental. This exploration should play an important role in the fabrication and applications of SMP materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40559.     

Characterization and strain‐energy‐function‐based modeling of the thermomechanical response of shape‐memory polymers

Shape‐memory polymers (SMPs) are an emerging class of active polymers that can be used on a wide range of reconfigurable structures and actuation devices. In this study, an epoxy‐based SMP was synthesized, and its thermomechanical behaviors were comprehensively characterized. The stress–strain behavior of the SMP was determined to be nonlinear, finite deformation in all regions. Strain‐energy‐based models were used to capture the complicated stress–strain behavior and shape‐recovery response of the SMP. Among various strain energy functions, the stretch‐based Ogden model provided the best fit to the experimental observations. Compared to the sophisticated models developed for SMPs, the strain‐energy‐based model was found to be reliable and much easier to use for practical SMP designs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41861.     

Linear Shape Memory Polyester with Programmable Splitting of Crystals

Shape memory polymers (SMPs)are widely used owing to their ability to change shapes under external stimuli. Conventional covalently crosslinked SMPs have limitations in biomedical applications. This article presents a linear shape memory biodegradable polyester without chemical crosslinks or multiblock structures. A new programming protocol is developed to split the crystals into two parts with different melting transitions through partial melting/recrystallization. The split crystals play different roles in fixation and recovery process to complete a shape memory cycle. The ratio between the partitioned crystals affects the fixed rate and recovery rate. The shape memory performance can be optimized by controlling the partial melting temperature and pre-stretching of the sample. Examples of complicated shape changes demonstrate the effectiveness of the proposed technique. The method is applicable to crystallizable linear polymers and has potential applications in implantation devices.     

New directions in the chemistry of shape memory polymers

The rapidly expanding field of shape memory polymers (SMPs) is driven by a growing number of potential applications, such as biomaterials, optics, and electronics. The basic concept involves polymers that can be trapped in a thermodynamically-unfavorable shape, then triggered by an external stimulus to return to their original shape, doing useful work in the process. Part of the attraction of using SMPs is that the energy released during actuation is stored in the polymer itself, rather than requiring an external force to change shape. This approach is beneficial for applications where external actuation is impossible or inconvenient. Polymers are also advantageous over shape memory metal alloys or ceramics in that there are endless combinations of functional groups and material properties to suit a variety of purposes, based on the monomers and polymerization conditions chosen. This advantage of SMPs is of particular interest in the development of materials with additional, desirable physicochemical attributes that are not necessarily coupled to the shape memory (SM) behavior itself. The SM behavior is quantitatively measured to facilitate comparison of various polymer systems, and researchers have used a number of defining parameters to guide the development and characterization of materials with extremely precise and reliable SM responses. In this review, recent trends in the structural or chemical characteristics of SMPs are explored, with an emphasis on how the molecular structure and functionality of each polymer affects its mechanical response.     

A novel type of shape memory polymer blend and the shape memory mechanism

A novel styrene-butadiene-styrene tri-block copolymer (SBS) and poly(?-caprolactone) (PCL) blend were introduced for its shape memory properties. Compared to the reported shape memory polymers (SMPs), this novel elastomer and switch polymer blend not only simplified the fabrication process but also offer a controllable approach for the study of mechanisms and the optimization of shape memory performances. Microstructures of this blend were characterized by differential scanning calorimetry (DSC), AFM microscope observation and tensile test. DSC results demonstrated the immiscibility between SBS and PCL. AFM images and stress-strain plot further confirmed the two-phase morphology within the blend. It was found that the SBS and PCL continuous phases contributed to the shape recovery and shape fixing performances, respectively. A detailed shape memory mechanism for this type of SMP system was then concluded and an optimized SMP system with both good recovery and fixing performances was designed from this mechanism.     

Engineering Porous Water‐Responsive Poly(PEG/PCL/PDMS Urethane) Shape Memory Polymers

Porous and bulk water‐responsive urethane‐based shape memory polymers (SMPs) containing poly(ethylene glycol) (PEG), poly(caprolactone), and poly(dimethylsiloxane) are fabricated. The copolymers are processed by electrospinning to achieve porous structures. Shape fixation and recovery are achieved via the solvation and recrystallization of the hydrophilic PEG switching segment. Mechanical testing is performed to determine the SMP functionality. Water uptake rate for porous SMP is found to be higher than bulk SMP partly due to higher surface area for water contact. This enables porous structure water‐responsive SMPs to recover faster compared to bulk SMPs. The water‐responsive SMP exhibits good extents of shape fixity and shape recovery when immersed in water (≈35 °C). Different actuation times can be achieved based on the total surface area and efficiency of water‐entry into the polymer.

     

Recent advance on constitutive models of thermal‐sensitive shape memory polymers

Shape memory polymers (SMPs) are a novel class of shape memory materials which can store a deformed (temporary) shape and recover an original (permanent) shape under a shape memory thermomechanical loading–unloading cycle. The deformation mechanisms of SMPs are very complicated, but the SMPs also have a lot of advantages and the widespread application value and prospect. So developing proper constitutive models that describe thermomechanical properties of SMPs and the shape memory effect is very challenging and of great theoretical and application value. Based on the deformation mechanisms and considerable experimental investigations of SMPs, researchers have developed many constitutive models. This article investigates the deformation mechanism and introduces the recent research advance of the constitutive models of thermal‐sensitive SMPs. Special emphases are given on the micromechanical constitutive relations in which the deformation is considered being based on the microstructure of the SMPs. Finally, the lack of research and prospects for further research are discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Shape‐memory behavior of thermally stimulated polyurethane for medical applications

Shape memory polymers (SMPs) have been of great interest because of their ability to be thermally actuated to recover a predetermined shape. Medical applications in clot extracting devices and stents are especially promising. We investigated the thermomechanical properties of a series of Mitsubishi SMPs for potential application as medical devices. Glass transition temperatures and moduli were measured by differential scanning calorimetry and dynamic mechanical analysis. Tensile tests were performed with 20 and 100% maximum strains, at 37 and 80°C, which are respectively, body temperature and actuation temperature. Glass transitions are in a favorable range for use in the body (35–75°C), with high glassy and rubbery shear moduli in the range of 800 and 2 MPa respectively. Constrained stress–strain recovery cycles showed very low hysteresis after three cycles, which is important to know for preconditioning of the material to ensure identical properties during applications. Isothermal free recovery tests showed shape recoveries above 94% for MP5510 thermoset SMP cured at different temperatures. One material exhibited a shape fixity of 99% and a shape recovery of 85% at 80°C over one thermomechanical cycle. These polyurethanes appear particularly well suited for medical applications in deployment devices such as stents or clot extractors. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3882–3892, 2007     

Shape Memory Study of Thermoplastic Segmented Polyurethane: Influence of Hard Segment

Thermally stimulated shape memorypolymers (SMP) are defined by their ability to store and recoverstrains when subjected to a particular thermo-mechanical cycle. The thermo-mechanical behavior of SMPs can be tailored by modifying the molecular structure of the polymer. In this article, the shape memory behavior of thermoplastic segmented polyurethane (TSPU) as a function of hard segment (HS) has been reported. The experimental results showed that tailoring of hard and soft segment is extremely necessary for TSPU showing shape memory behavior. The thermo-mechanical properties of TSPU with four different concentrations of hard segment viz. 58.7, 47.9, 37.5, and 31.0% have been studied in this article. TSPU with 58.7% of hard segment content would not able to elongate even up to 30% in experimental condition. However, all other three samples show good shape memory behavior.     

Synthesis and properties of biodegradable supramolecular polymers based on polylactide‐block‐poly(δ‐valerolactone)‐block‐polylactide triblock copolymers

Biodegradable supramolecular polymers (SMPs) were synthesized by the end‐functionalization of polylactide‐block‐poly(δ‐valerolactone)‐block‐polylactide (PLA–PVL–PLA) triblock copolymers with 2‐ureido‐4[1H]‐pyrimidinone (UPy) self‐complementary quadruple hydrogen‐bonding units. The end‐functionalized PLA–PVL–PLA copolymers exhibit the typical characteristics of thermoplastic elastomers. Thermal properties, crystallization behavior, crystalline structure and other properties of SMPs can be adjusted by changing the length and stereostructure of PLA blocks. The UPy groups retard the crystallization of PLA and PVL blocks, and the crystallization of PVL blocks is also depressed with increasing PLA blocks. Tensile testing reveals that the prepared SMPs present excellent mechanical properties, and dynamic mechanical analysis indicates that the heat resistance of l ‐SMPs is better than that of d ,l ‐SMPs. Shape memory property of SMPs was also studied, and the recovery ratio of SMPs with PDLLA blocks can reach 100%. The recovery ratio of l ‐SMPs is depressed as the crystallizable PLLA blocks increase. This study has systemically investigated the effect of the composition, stereostructure and crystallizability of PLA blocks on the properties of SMPs, which would provide potential approaches for the synthesis of biodegradable SMPs with tunable properties. © 2017 Society of Chemical Industry     

Shape memory properties of olefin block copolymer (OBC)/poly(ɛ‐caprolactone) (PCL) blends

Conventionally, the chemically crosslinked shape memory polymer (SMP) blends are hard to recycle due to their network structure. Herein, the environmental SMP blends of olefin block copolymer (OBC), a unique thermoplastic elastomer, and poly(?‐caprolactone) (PCL) were physically crosslinked. Dicumyl peroxide was used as the compatibilizer to improve their miscibility, as evidenced by the reduced dispersed domain size of PCL in the OBC matrix and the increased complex viscosity. The peroxide modified OBC/PCL blend conferred enhanced tensile properties, increased dynamic storage modulus, increased crystallization temperature, and higher recovery stress. The shape memory behaviors of OBC/PCL blends predeformed under two different predeformation temperatures (30 and 65 °C) were investigated. The recovery stress showed respective maximum peak values corresponding to their predeformation temperatures. In addition, the modified blends gave the better shape memory performance at 65 °C. Besides the peroxide modification approach, a precycle training process via prestretching the samples and reducing the mechanical hysteresis was implemented to improve shape memory performance further. This is the first work on the OBC‐based SMP blends to enhance shape memory performance by combining the chemical modification using added peroxide compatibilizer and the process modification using a precycle training process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45475.