Enhanced mechanical properties of acrylate based shape memory polymer using grafted hydroxyapatite

In the present study, the effect of grafted and ungrafted hydroxyapatite (HAp) filler on the mechanical properties of acrylate based shape memory polymer (SMP) composite is reported. HAp is grafted with polyethylene glycol methacrylate (PEGMA) monomer to avoid agglomeration and the same is embedded as reinforcement in tBA – PEGDMA matrix (70 wt% tBA: tert-butyl acrylate +30 wt% PEGDMA: polyethylene glycol dimethacrylate). The grafting process improved the interfacial interactions of the particles, dispersed in the polymer system and subsequently enhanced the mechanical properties of the shape memory polymer composites. The morphology of HAp particles is investigated by field emission scanning electron microscopy. The mechanical properties of SMP composites are evaluated at room temperature and above glass transition temperature (Tg) with grafted and ungrafted HAp particles. The addition of grafted HAp significantly improved the tensile strength (40%) and shape recovery rate (25%) of the SMP composite when compared to the SMP composite containing ungrafted HAp. SMP composite containing grafted HAp exhibited higher cell viability compared to the neat SMP and the SMP composite containing ungrafted HAp.     

Mechanical and shape‐memory behavior of shape‐memory polymer composites with hybrid fillers

Shape‐memory polymer (SMP) materials have several drawbacks such as low strength, low stiffness and natural insulating tendencies, which seriously limit their development and applications. Much effort has been made to improve their mechanical properties by adding particle or fiber fillers to reinforce the polymer matrix. However, this often leads to the mechanical properties being enhanced slightly, but the shape‐memory effect of reinforced SMP composites being drastically reduced. The experimental results reported here suggested that the mechanical resistive loading and thermal conductivity of a composite (with hybrid filler content of 7.0 wt%) were improved by 160 and 200%, respectively, in comparison with those of pure bulk SMP. Also, the glass transition temperature of the composite was enhanced to 57.28 °C from the 46.38 °C of a composite filled with 5.5 wt% hybrid filler, as determined from differential scanning calorimetry measurements. Finally, the temperature distribution and recovery behavior of specimens were recorded with infrared video in a recovery test, where a 28 V direct current circuit was applied. The effectiveness of carbon black and short carbon fibers being incorporated into a SMP with shape recovery activated by electricity has been demonstrated. These hybrid fillers were explored to improve the mechanical and conductive properties of bulk SMP. Copyright © 2010 Society of Chemical Industry     

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.     

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.     

Shape‐memory polyurethane/multiwalled carbon nanotube fibers

Shape‐memory polyurethane/multiwalled carbon nanotube (SMP–MWNT) composites with various multiwalled carbon nanotube (MWNT) contents were synthesized, and the corresponding SMP–MWNT fibers were prepared by melt spinning. The influence of the MWNT content on the spinnability, fracture morphology, thermal and mechanical properties, and shape‐memory behavior of the shape‐memory polymer was studied. The spinning ability of SMP–MWNTs decreased significantly with increasing MWNT content. When the MWNT content reached 8.0 wt %, the fibers could not be produced because of the poor rheological properties of the composites. The melt‐blending, extrusion, and melt‐spinning processes for the shape‐memory fiber (SMF), particularly at low MWNT contents, caused the nanotubes to distribute homogeneously and preferentially align along the drawing direction of the SMF. The crystallization in the SMF was promoted at low MWNT contents because it acted as a nucleation agent. At high MWNT contents, however, the crystallization was hindered because the movement of the polyurethane chains was restricted. The homogeneously distributed and aligned MWNTs preserved the SMF with high tenacity and initial modulus. The recovery ratio and recovery force were also improved because the MWNTs helped to store the internal elastic energy during stretching and fixing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Short glass fiber reinforced radiation crosslinked shape memory SBS/LLDPE blends

The poly(styrene‐b‐butadiene‐b‐styrene) triblock copolymer (SBS) and linear low density polyethylene(LLDPE) were blended and irradiated by γ‐rays to prepare shape memory polymer(SMP). Various amounts of short glass fiber (SGF) were filled into SMP to form a novel shape memory SGF/SBS/LLDPE composite. The effect of SGF on the shape memory SGF/SBS/LLDPE composite was studied in terms of mechanical, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and shape memory effects. It is found that the SGF act as reinforcing fillers and significantly augment the glassy and rubbery stated moduli, tensile strength and shape memory properties. When SGF content is <2.0 wt %, full recovery can be observed after only several minutes at different temperatures and shape recovery speed reduces as the SGF content increases. The shape recovery time decreases as the temperature of the shape memory test increases and the shape recovery rate decreases with increment of cycle times. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40691.     

Thermomechanical studies of aluminum nitride filled shape memory polymer composites

High thermal conductivity polyurethane shape memory polymer (SMP) composites filled with aluminum nitride (AlN) were fabricated, and their thermal and thermomechanical properties were studied. The purpose of this microstructure is to improve the thermal properties of the SMPs at low filler content. Morphology of AlN filler in polyurethane SMP matrix and the resulting thermal conductivity was also investigated. Thermal studies have shown that AlN is an effective filler for reinforcement of the polyurethane SMP and that it does not deteriorate the stable physical crosslink structure of the polyurethane, which is necessary to store the elastic energy in the service process of the shape memory material. The thermal conductivities of these SMP composites in relation to filler concentration and temperature were investigated, and it was found that the thermal conductivity can increase up to 50 times in comparison with that of the pure SMP. Furthermore, differential scanning calorimetry tests have shown a significant decrease in the glass transition temperature of the switching segment. Dynamic mechanical studies have shown that the storage modulus of the composites increase with higher AlN content in both glassy and rubbery state. Damping peak decreases and also the curve of damping becomes broader with increasing filler content. Strain fixity rate which expresses the ability of the specimens to fix their strain has been improved slightly in the presence of AlN filler but the final recovery rate of the shape memory measurement has decreased evidently. POLYM. COMPOS., 28:287–293, 2007. © 2007 Society of Plastics Engineers     

Dynamic mechanical properties of sandwich‐structured epoxy beam composites containing poly(ethyleneterephthalate)/poly(ethyleneglycol) copolymer with shape memory effect

To make smart vibration‐controlling composite laminate, a few poly(ethylene terephthalate) (PET) and poly(ethylene glycol) (PEG) copolymers with shape memory ability were prepared. After selecting the best composition of PET–PEG copolymer in mechanical properties, a crosslinking agent such as glycerine, sorbitol, or maleic anhydride (MA) was included for crosslinked copolymer, followed by analysis of its effect on mechanical, shape memory, and damping properties. The highest shape recovery was observed for copolymer with 2.5 mol % of glycerine, and the best damping effect indicating vibration control ability was from copolymer with 2.5 mol % of sorbitol. With the optimum copolymers in hand, sandwich‐structured epoxy beam composites fabricated from an epoxy beam laminate and crosslinked PET–PEG copolymer showed that impact strength increased from 1.9 to 3.7 times depending on the type of copolymer, and damping effect also increased as much as 23 times for the best case compared to epoxy laminate beam alone. The resultant sandwich‐structured epoxy beam composite can be utilized as structural composite material with vibration control ability, and its glass transition temperature can be controlled by adjustment of PET, PEG, or crosslinking agent composition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3141–3149, 2003     

Analysis of the isothermal mechanical response of a shape memory polymer rheological model

In this paper, we derive the isothermal mechanical response of a 4‐element rheological model for shape memory polymers (SMP) in the context of (i) constant stress, (ii) constant strain, (iii) constant stress rate, (iv) constant strain rate, (v) periodic strain. The effect of shape memory strain (modeled by a friction element) and the temperature dependence of the material properties on the SMP response are examined for a polyurethane shape memory polymer of the polyester polypole series. In particular, it is possible to identify a threshold frequency during periodic loading, near which the damping capacity of the SMP is strongly affected by an increasing shape memory strain. On the other hand, when the applied frequency is much greater than the threshold value, an increasing shape memory strain ceases to have any effect on the damping. It is also shown that at a given frequency (significantly greater than the threshold value), the damping capacity as a function of temperature attains a maximum. While this maximum value is frequency‐dependent (being inversely proportional), the temperature at which the maximum is attained is frequency‐independent, and is analytically shown to be the glass transition temperature.     

Thermomechanical characterization of a shape memory polymer based self-repairing syntactic foam

While the current self-healing approaches such as micro-capsules, hollow fibers, thermally reversible covalent bonds, ionomers, incorporation of thermoplastic particles, etc., are very effective in self-healing micro-length scale damage, self-healing of structural scale or macro-length scale damage remains one of the grand challenges facing the self-healing community. We believe that self-healing of structural damage may need multiple steps, at least two steps: close then heal (CTH), similar to the biological healing of wounds in the skin. In a previous study [1], it has been proven that the confined shape recovery functionality of a shape memory polymer (SMP) based syntactic foam can be utilized to repair structural damage such as impact damage repeatedly, efficiently, and almost autonomously. The purpose of this study is to investigate the effect of various design parameters on the closing efficiencies of both the pure SMP and the SMP based syntactic foam. A systematic test program is implemented, including glass transition temperature (T_g) determination by dynamic mechanical analysis (DMA), isothermal compressive constitutive behavior at various temperatures, and stress-controlled uniaxial compression programming and shape recovery. During thermomechanical cycle testing, two stress levels are utilized for programming and three confinement conditions (fully confined, partially confined, and free) are investigated for shape recovery. It is found that the programming stress is restored under confined recovery conditions, which helps in fully closing the crack; the foam shifts the T_g higher and increases the stiffness at temperatures above the T_g; higher programming stresses lead to slightly higher shape fixity but lower shape recovery in free recovery cases; a higher programming stress also results in a higher peak stress for confined recovery conditions; while the peak stress recovered is controlled by thermal stress, the final stress recovered is controlled by the programming stress, which is stored and recovered using an entropic mechanism. This study lays a solid foundation for using shape memory polymer based composites to self-repair macro-length scale damage.     

Molecular weight influence on shape memory effect of shape memory polymer blend (poly(caprolactone)/styrene-butadiene-styrene)

The shape memory effect (SME) does not only concern the macroscopic structure. It concerns also the polymer structure at morphological, macromolecular, and molecular scales. This effect may depend on different physicochemical properties like morphology heterogeneity, chain rigidity, steric hindrance, chain polarity, free volume, cross-linking or entanglement density, molecular shape and weight, and so on. Hence, finding the relationship between the SME and these properties is very important. This can help to obtain the knowledge about the phenomenon origin and mechanism. One of the basic polymer properties, which can have direct SME, may be the molecular weight (M_w ). The question here is: If the M_w of a shape memory polymer (SMP) changes, for different reasons like degradation, what will be the effect of this change on its SME. In order to answer to this question, the investigation is focused on an SMP blend of 40% poly(ɛ-caprolactone) (PCL) and 60% styrene-butadiene-styrene (SBS). Then, enzymatic hydrolysis is performed on this blend to change its M_w . It is shown that this change is only related to the variation in the M_w of PCL. After that, different samples with a distinct average M_w are prepared and characterized by various experimental methods. Shape memory tests are performed on these blends, and the recovery rate (R_r ) for each of them is determined. It is found that when M_w of PCL decreases, its degree of crystallinity, its glass transition, and its melting temperatures, corresponding to the PCL phase, increase. However, the elongation at break of the blend declines with the reduction in M_w . The tests show that the alteration in the blend's M_w influences its SME. Indeed, R_r of the (PCL/SBS) mixture drops with the decrease in M_w of PCL.     

Effect of strain hardening of shape memory polymer fibers on healing efficiency of thermosetting polymer composites

Recently, shape memory polymer fibers (SMPFs) have been used in a biomimetic two-step (Close-Then-Heal) self-healing system for healing macroscopic cracks. The objective of this study was to investigate the effect of cold-drawing programming of SMPFs on the healing efficiency of conventional thermosetting polymer composites and the possibility of healing wide-opened crack by localized heating. To achieve the objective, continuous SMPF strand reinforced conventional epoxy composite beam specimens, which were dispersed with thermoplastic particles, were prepared. The SMPF strands were cold-drawn to various pre-strain levels before casting the polymer matrix. Repeated fracture/healing test was conducted by uniaxial tension. It is found that the composites were able to repeatedly heal macroscopic cracks. Strain-hardening by cold-drawing increased the healing efficiency considerably. It was demonstrated that healing can be achieved by heating locally surrounding the cracked region. The mechanism for the enhanced recovery stress was due to cold-drawing induced molecular alignment and formation of some perfect crystals in the hard segment domain of the SMPF.     

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.     

Melt spun thermoresponsive shape memory fibers based on polyurethanes: Effect of drawing and heat‐setting on fiber morphology and properties

Thermoresponsive shape memory (SMP) fibers were prepared by melt spinning from a polyester polyol‐based polyurethane shape memory polymer (SMP) and were subjected to different postspinning operations to modify their structure. The effect of drawing and heat‐setting operations on the shape memory behavior, mechanical properties, and structure of the fibers was studied. In contrast to the as‐spun fibers, which were found to show low stress built up on straining to temporary shape and incomplete recovery to the permanent shape, the drawn and heat‐set fibers showed significantly higher stresses and complete recovery. The fibers drawn at a DR of 3.0 and heat‐set at 100°C gave stress values that were about 10 times higher than the as‐spun fibers at the same strain and showed complete recovery on repeated cycling. This improvement was likely due to the transformation brought about in the morphology of the permanent shape of the SMP fibers from randomly oriented weakly linked regions of hard and soft segments to the well‐segregated, oriented and strongly H‐bonded regions of hard‐segments. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2172–2182, 2007     

Modeling the effective properties and thermomechanical behavior of SMA‐SMP multifunctional composite laminates

The research work presents the modeling of effective properties and thermo‐mechanical behavior of shape memory fiber (SMF) and shape memory polymer (SMP) composite laminates using micromechanical approaches based on the method of mixtures (MOM) and method of cells (MOC). The fiber is made of a nickel‐titanium (Ni‐Ti) shape memory alloy (SMA), while the matrix consists of a shape memory thermoset epoxy polymer (SMP). The use of an SMP matrix provides large strain compatibility with the SMA fiber, while being active at high temperatures without losing its elastic properties. Additionally, the SMP matrix is also able to produce similar pseudoelastic and shape memory effects, which are noticed in SMAs. In the analysis, a two step homogenization scheme is followed. In the first step the effective properties of each layer are determined via a micromechanics approach with iso‐strain conditions. In the second step the effective properties of the SMF‐SMP composite are computed making a thin plate theory assumption, which takes into account the transverse shear deformations. The possible elastic couplings for SMF‐SMP laminates are discussed, and the laminate force and moment resultants are computed for various laminate configurations. The analysis takes into account the effects of phase transformations and the resulting change in the fiber–matrix modulus. The results have been compared by considering different fiber volume fractions, temperatures, fiber orientations, and lamina stacking sequences. The results show that adaptive SMA‐SMP composites laminates can be developed that provide shape controllability via tunable laminate stiffnesses leading to optimal response. Furthermore, the work presents the necessary framework for a reliable and efficient analysis of SMA‐SMP laminates for practical applications. The theory can be directly used in established plate and shell formulations of finite element analysis. Finally, the variations in force and moment resultants with respect to fiber orientations and stacking sequences are presented, which are useful to study the bending and buckling characteristics of active composites for shape control of adaptive structures. The work concludes that efficient adaptive laminate development for high performance composite applications, exhibiting large shape adaptivity, high stresses, and increased stiffness, are feasible as compared to SMA composites without active matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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     

Effects of stretch induced softening to the free recovery behavior of shape memory polymer composites

During a cyclic tension test, many elastomeric materials exhibit an appreciable softening in their mechanical properties resulting from the previous stretch, known as the Mullins effect. This paper explores the influence of the stretch induced softening effect to the free recovery behavior of an acrylate shape memory polymer (SMP) composite by incorporating carbon black (CB) as filler materials. The observed softening effect in this SMP composite is considered to be a consequence of stretch induced alternation of filler–polymer interactions inside the composite. Further experiments find that a larger prior stretch gives a larger increase in material softening, which in turn decreases the shape recovery speed. To capture the experimental observations, a multi-branch one dimensional (1D) model is applied, where the modulus in the equilibrium branch is modeled to decrease with stretching deformation following a damage-like softening function. It is found that the loss in modulus due to softening consequently reduces the driving force for recovery and thus results in a slow recovery. Parametric studies further demonstrate that the discounted shape recovery speed will finally reach a saturated level when gradually increasing the programmed strain level in a shape memory cycle.     

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.     

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.     

Progress in shape memory epoxy resins

This review analyses the progress in the field of shape memory epoxy resins (SMEPs). Partial crystallisation and vitrification are the basis of shape memory effect in SMEPs. Several synthetic approaches for SMEPs, their composites and foams have been reviewed. Strategically incorporated thermally reversible segments induce the shape memory effect in epoxy resins. By varying the nature and concentration of shape memory segments, wide range of shape memory properties and transition temperatures (shape memory temperatures) can be achieved. Triple shape memory, self-healability and electroactive capability are some of the additional features that can be created in SMEPs. Among the thermoset resins, shape memory epoxies are the most attractive systems because of the ease of processability, composite forming properties and dimensional stability. Shape memory epoxy polymers that can be processed into elastic memory composites are candidate materials in the processing of many smart engineering systems. In this background, a review consolidating the progress in SMEP has contemporary relevance. The present article takes a stock of the trend in SMEP with a view to assess the direction of future initiatives in this area. It is concluded that there is tremendous scope for research leading to technological evolution in the field of SMEP.