Stress memory of a thermoset shape memory polymer

The performance of stress recovery and shape recovery are equally important for high performance shape memory polymers (SMPs) in emerging applications. However, unlike shape recovery, stress recovery does not always follow a monotonic behavior, i.e., “stress plateau,” “stress overshoot,” and “stress undershoot” can be observed. In order to reveal the complicated stress memorization and recovery behavior, this study employs a phenomenological model which considers the recovery stress as the sum of residual programming stress, memorized stress, thermal stress, and relaxed stress for amorphous crosslinked SMPs. This model is demonstrated by a stress recovery experiment in which a polystyrene based SMP was programmed at two prestrain levels above the glass transition temperature, i.e., 20% (neo‐Hookean hyperelastic region) and 50% (strain‐hardening region), and two fixation temperatures, i.e., 20°C (below T_g) and 45°C (within the T_g region), respectively. In addition, a clear distinction between the memorized stress and recovery stress is presented. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42112.     

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     

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     

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     

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     

Effect of cycling frequency and self‐heating on fatigue behavior of reinforced and unreinforced thermoplastic polymers

An experimental study was conducted to evaluate the effect of frequency and self‐heating on fatigue behavior of two unreinforced and two short glass fiber reinforced thermoplastic polymers. Load‐controlled fatigue tests were conducted under fully reversed (R = ?1) and R = 0.1 conditions with specimens loaded in either longitudinal or transverse direction to the mold flow direction. Effect of frequency on fatigue life was evaluated at 23 and 125°C and for a range of frequencies between 0.063 and 20 Hz. Incremental step frequency tests were also performed at different stress ratios and stress levels. Surface temperature rise was found to be material, frequency, and stress level dependent. Three energy‐based models were applied to the incremental step frequency data and relationships were developed for each material to estimate surface temperature rise as a function of test frequency and stress level. Relationships were also developed to assess critical frequency for the unreinforced thermoplastics at a given stress level above which surface temperature does not stabilize. POLYM. COMPOS., 55:2355–2367, 2015. © 2015 Society of Plastics Engineers     

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.     

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.     

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.     

Shape‐memory bioresorbable terpolymer composite with antirestenotic drug

Shape‐memory polymers (SMPs) that combine shape‐memory, biodegradability, and controlled drug release properties are very promising for medical and pharmaceutical application. Moreover, incorporation of antirestenotic drug into SMP biodegradable stent seems to be an interesting solution because of possibility to combine the mechanical support that provides stent and also drug elution. The aim of our study was to analyze the effect of incorporation of sirolimus into poly(l ‐lactide‐co‐glycolide‐co‐trimethylene carbonate) on physicochemical and mechanical properties, degradation, and shape‐memory effect of the terpolymer. For this purpose, sirolimus was incorporated into the terpolymer by injection molding method. It has been demonstrated that drug‐free terpolymer after injection molding characterized insignificant changes in terpolymer composition. Degradation of materials during processing was not observed. Incorporation of drug molecules did not change shape‐memory properties of terpolymer. ¹H‐ and ¹³C‐NMR spectra of poly(lactide‐co‐glycolide‐co‐trimethylene carbonate) confirmed that changes during degradation were similar for terpolymer and terpolymer with sirolimus. Sustained and regular release of sirolimus was observed. The developed material presents potential for biomedical and pharmaceutical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41902.     

Creep characterization of vapor‐grown carbon nanofiber/vinyl ester nanocomposites using a response surface methodology

The effects of selected factors such as vapor‐grown carbon nanofiber (VGCNF) weight fraction, applied stress, and temperature on the viscoelastic responses (creep strain and creep compliance) of VGCNF/vinyl ester (VE) nanocomposites were studied using a central composite design (CCD). Nanocomposite test articles were fabricated by high‐shear mixing, casting, curing, and post curing in an open‐face mold under a nitrogen environment. Short‐term creep/creep recovery experiments were conducted at prescribed combinations of temperature (23.8–69.2°C), applied stress (30.2–49.8 MPa), and VGCNF weight fraction (0.00–1.00 parts of VGCNF per hundred parts of resin) determined from the CCD. Response surface models (RSMs) for predicting these viscoelastic responses were developed using the least squares method and an analysis of variance procedure. The response surface estimates indicate that increasing the VGCNF weight fraction marginally increases the creep resistance of the VGCNF/VE nanocomposite at low temperatures (i.e., 23.8–46.5°C). However, increasing the VGCNF weight fraction decreased the creep resistance of these nanocomposites for temperatures greater than 50°C. The latter response may be due to a decrease in the nanofiber‐to‐matrix adhesion as the temperature is increased. The RSMs for creep strain and creep compliance revealed the interactions between the VGCNF weight fraction, stress, and temperature on the creep behavior of thermoset polymer nanocomposites. The design of experiments approach is useful in revealing interactions between selected factors, and thus can facilitate the development of more physics‐based models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42162.     

Shape‐memory behavior of high‐strength amorphous thermoplastic poly(para‐phenylene)

The purpose of this study was to investigate the shape‐memory behavior of poly(para‐phenylene) (PPP) under varying programming temperatures, relaxation times, and recovery conditions. PPP is an inherently stiff and strong aromatic thermoplastic, not previously investigated for use as a shape‐memory material. Initial characterization of PPP focused on the storage and relaxation moduli for PPP at various frequencies and temperatures, which were used to develop continuous master curves for PPP using time–temperature superposition (TTS). Shape‐memory testing involved programming PPP samples to 50% tensile strain at temperatures ranging from 155°C to 205°C, with varying relaxation holds times before cooling and storage. Shape‐recovery behavior ranged from nearly complete deformation recovery to poor recovery, depending heavily on the thermal and temporal conditions during programming. Straining for extended relaxation times and elevated temperatures significantly decreased the recoverable deformation in PPP during shape‐memory recovery. However, PPP was shown to have nearly identical full recovery profiles when programmed with decreased and equivalent relaxation times, illustrating the application of TTS in programming of the shape‐memory effect in PPP. The decreased shape recovery at extended relaxation times was attributed to time‐dependent visco‐plastic effects in the polymer becoming significant at longer time‐scales associated with the melt/flow regime of the master curve. Under constrained‐recovery, recoverable deformation in PPP was observed to have an exponentially decreasing relationship to the bias stress. This study demonstrated the effective use of PPP as a shape‐memory polymer (SMP) both in mechanical behavior as well as in application. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42903.     

Fully bio‐based poly(ɛ‐capolactone)/poly(lactide) alternating multiblock supramolecular polymers: Synthesis,crystallization behavior,and properties

Supramolecular poly(?‐capolactone)/poly(lactide) alternating multiblock copolymers were prepared by UPy‐functionalized poly(lactide)‐b‐ poly(?‐capolactone)‐b‐ poly(lactide) copolymers. The prepared supramolecular polymers (SMPs) exhibit the characteristic properties of thermoplastic elastomers. The stereo multiblock SMPs (sc‐SMPs) were formed by blending UPy‐functionalized poly(l ‐lactide)‐b‐ PCL‐b‐ poly(l ‐lactide) (l ‐SMPs) and UPy‐functionalized poly(d ‐lactide)‐b‐ PCL‐b‐ poly(d ‐lactide) (d ‐SMPs) due to stereocomplexation of the PLLA and PDLA blocks. Sc‐SMPs with low content of d ‐SMPs (≤20%) are transparent, elastic solids, while those having high d ‐SMPs content are opaque, brittle solids. The effects of l ‐SMPs/d ‐SMPs mixing ratios on thermal, crystallization behaviors, crystal structure, mechanical and hydrophilic properties of sc‐SMPs were deeply investigated. The incorporation of UPy groups depresses the crystallization of polymer, and the stereocomplex formation accelerates the crystallization rate. The used initiator functionalized polyhedral oligomeric silsesquioxanes causes a different effect on the crystallization of PLA and PCL blocks. The tensile strength and elongation at break of l _d /d _d ‐SMPs (d represents the initiator diethylene glycol) are significantly larger than that of l _p /d _p ‐SMPs (p represents the initiator polyhedral oligomeric silsesquioxanes), and their heat resistance and hydrophilicity can be also modulated by the l ‐SMPs/d ‐SMPs mixing ratios and the different initiators. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45575.     

Silicone membranes to inhibit water uptake into thermoset polyurethane shape‐memory polymer conductive composites

Electroactive shape memory polymer (SMP) composites capable of shape actuation via resistive heating are of interest for various biomedical applications. However, water uptake into SMPs will produce a depression of the glass transition temperature (T_g) resulting in shape recovery in vivo. While water actuated shape recovery may be useful, it is foreseen to be undesirable during early periods of surgical placement into the body. Silicone membranes have been previously reported to prevent release of conductive filler from an electroactive polymer composite in vivo. In this study, a silicone membrane was used to inhibit water uptake into a thermoset SMP composite containing conductive filler. Thermoset polyurethane SMPs were loaded with either 5 wt % carbon black or 5 wt % carbon nanotubes, and subsequently coated with either an Al₂O₃‐ or silica‐filled silicone membrane. It was observed that the silicone membranes, particularly the silica‐filled membrane, reduced the rate of water absorption (37°C) and subsequent T_g depression versus uncoated composites. In turn, this led to a reduction in the rate of recovery of the permanent shape when exposed to water at 37°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41226.     

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.

     

Preparation of 2‐(dimethylamino) ethyl methacrylate copolymer micelles for shape memory materials

Researchers are actively developing shape memory polymers (SMPs) for smart biomaterials. This paper reports a new SMP system synthesized from biocompatible 2‐(dimethylamino) ethyl methacrylate (DMAEMA), butyl acrylate (BA) and tri(ethylene glycol) divinyl ether (TDE). Preliminary results show that the DMAEMA‐co‐BA‐co‐TDE copolymers form micelles in aqueous solution due to chemical crosslinking and hydrophobicity. The micelle size decreased with the increase in the BA content since the hydrophobicity of copolymers increases with the increase of BA content. The resulting polymer films contain–N(CH₃)₂ functional groups for further biomaterial applications. The thermal stability of DMAEMA‐co‐BA‐co‐TDE copolymers is determined by the DMAEMA structure and content. Moreover, the copolymers form micro‐phase‐separated structures containing a reversible amorphous soft phase, and the storage moduli decreases significantly around T_g. Therefore, good thermal‐induced shape memory effects are achieved in the DMAEMA‐co‐BA‐co‐TDE copolymers by adjusting the BA content. This work proposes a new strategy for designing smart biomaterials using a biocompatible monomer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42312.     

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.     

An investigation of stress oscillation in poly(butylene succinate‐co‐cyclohexanedimethylene succinate)

Biodegradable poly(butylene succinate‐co‐cyclohexanedimethylene succinate) (PBCS) was synthesized via polycondensation. The composition of PBCS was characterized by ¹H‐nuclear magnetic resonance (¹H‐NMR). By incorporation of 20 wt% of cyclohexanedimethylene succinate, stress oscillation behavior in stress–strain curve was observed during cold drawing. The stress was no longer stable, but exhibited constantly periodic fluctuations. Morphology and crystalline structure of oscillatory portion were evaluated by scanning electron microscopy, and X‐ray diffraction (XRD), respectively. The melting behavior was studied using differential scanning calorimetry (DSC). The surface morphology of oscillatory portion presented alternating opaque and transparent bands, which were perpendicular to the cold‐drawing direction. By comprehensive analysis of stress–strain curve, surface morphology, XRD, and DSC, the formation of stress oscillation was discussed. To describe stress oscillation, a new mathematical model was proposed to simulate stress oscillation and its viscoelastic behaviors were well explained. The novelty of the mathematical model was that new oscillatory cells consisting of a dashpot with free inextensible strings were adopted to instead of fiber bundle cells. POLYM. ENG. SCI., 55:966–974, 2015. © 2014 Society of Plastics Engineers     

Surface grafting of carbon fibers with artificial silver‐nanoparticle‐decorated graphene oxide for high‐speed electrical actuation of shape‐memory polymers

Poor heat conduction in the interface between the carbon fiber and polymer matrix is a problem in the actuation of shape‐memory polymer (SMP) composites by Joule heating. In this study, we investigated the effectiveness of grafting silver‐nanoparticle‐decorated graphene oxide (GO) onto carbon fibers to improve the electrothermal properties and Joule‐heating‐activated shape recovery of SMP composites. Self‐assembled GO was grafted onto carbon fibers to enhance the bonding of the carbon fibers with the polymeric matrix via van der Waal's forces and covalent crosslinking, respectively. Silver nanoparticles were further self‐assembled and deposited to decorate the GO assembly, which was used to decrease the thermal dissimilarity and facilitate heat transfer from the carbon fiber to the polymer matrix. The carbon fiber was incorporated with SMP to achieve the shape recovery induced by Joule heating. We found that the silver‐nanoparticle‐decorated GO helped us achieve a more uniform temperature distribution in the SMP composites compared to those without decoration. Furthermore, the shape‐recovery behavior and temperature profile during the Joule heating of the SMP composites were characterized and compared. A unique synergistic effect of the carbon fibers and silver‐nanoparticle‐decorated GO was achieved to enhance the heat transfer and a higher speed of actuation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41673.     

Rheological behavior of coir‐fiber‐filled polypropylene composites at constant shear stress

The rheological behavior of coir‐fiber‐filled polypropylene (PP) composite has been studied at constant shear stress. The shear stress versus shear rate relationship for the composite follows power law model of viscous flow. Unlike similar studies in the literature, the viscosity is treated as a stress‐independent parameter, which increases with the increase of fiber loading; but decreases with the rise of temperature. The SEM reveals that the fibers are loosely bound to the polymer matrix and the outer surface of the composite is rough and irregular, making it susceptible to high friction with the wall of the flow channel. With analogy to nth order chemical reaction, new formula has been derived for the activation energy of viscous flow, which is found to increase with the increase in the fiber content. The die‐swell ratio decreases with the increase of fiber loading, but increases with the rise of temperature. The elastics parameters of the composite such as the recoverable shear strain, the first normal stress difference, and the elastic strain induced by the stored energy in the capillary reservoir have been estimated based on the die‐swell data. POLYM. COMPOS., 36:51–61, 2015. © 2014 Society of Plastics Engineers