Viscoelastic characteristics of shape memory polymers

Shape memory polymers (SMPs) can keep a temporary state and subsequently recover to the original shape through a prescribed thermomechanical process. Although different theoretical models have been presented, the viscous effects were seldom considered. This article aims to provide an insight into the viscoelastic property of SMPs and its effect on the functional realization. Systematic thermomechanical experiments were performed. Special considerations were focused on the viscoelastic response of SMPs in the vicinity of the glass transition temperature T_g. The relations between shape switching transition temperature T_tran and T_g were also discussed. The results confirm that T_tran departs from T_g due to the viscoelastic effect and does not keep a constant value during heating and cooling processes. The viscoelastic effect reaches to maximum value at T_g, then decreases slowly at cooling and quickly at heating. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

3D printing of shape memory polymers

Shape memory polymers (SMPs) are polymers which ''remember'' their original shape and can return to it after deformation, if an external stimulus—often an increased temperature – is applied. Some SMPs can be 3D printed, typically by fused deposition modeling (FDM). The most well-known SMP is poly(lactic acid), which belongs to the most often used materials in FDM 3D printing. There are; however, many more SMPs which can be 3D printed to combine the possibilities to prepare new, sophisticated shapes with the opportunity to restore these shapes after undesirable or intentional deformation. This review gives an overview of several 3D printable SMPs, their mechanical characteristics and their possible applications.     

Facile control of high temperature shape memory polymers

Glass transition temperature (T_g) is crucial in determining application areas of high temperature shape memory polymers (SMPs), but some T_gs are difficult or uneconomic to be obtained. Here we introduce a facile way to prepare high temperature SMPs with controllable T_gs from 183 to 230 °C by copolymerization of polyimides, and relationships between T_gs and diamine components of the shape memory copolyimides agree with Fox Equation. These copolyimides can fix temporary shape and return to original shape nicely, and the possible mechanisms of their high shape fixity and shape recovery are analyzed on the basis of thermomechanical properties and molecular structures. The copolymerization of shape memory polyimides has offered an effective way to obtain high temperature SMPs with desired properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44902.     

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.     

Synthesis of high temperature polyaspartimide-urea based shape memory polymers

Thermally activated shape memory polymers (SMPs) have attracted great interest in recent years for application in adaptive shape-changing (morphing) aero structures. However, these components require materials with transition temperatures well above the glass transition temperatures of most widely available SMPs while also maintaining processability and property tailorability. In the present study, a series of novel polyaspartimide-urea based polymers are synthesized and characterized. The glass transition temperature and shape memory properties are varied using a diisocyanate resin creating a urea crosslinking moiety between the polyaspartimide chains. Overall, a family of high temperature SMPs was synthesized and characterized showing high thermal stability (>300 °C), toughness, strong shape memory effects, and tailorable properties.     

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.     

Facile tailoring of thermal transition temperatures of epoxy shape memory polymers

A critical parameter for a shape memory polymer (SMP) lies in its shape memory transition temperature. For an amorphous SMP polymer, it is highly desirable to develop methods to tailor its T_g, which corresponds to its shape memory transition temperature. Starting with an amine cured aromatic epoxy system, epoxy polymers were synthesized by either reducing the crosslink density or introducing flexible aliphatic epoxy chains. The thermal and thermomechanical properties of these epoxy polymers were characterized by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). All the crosslinked epoxy polymers with T_g's above room temperature were found to possess shape memory properties. Overall, our approach represents a facile method to precisely tune the T_g of epoxy SMP polymers ranging from room temperature to 89 °C.     

Study of nanoreinforced shape memory polymers processed by casting and extrusion

Multi‐walled carbon nanotubes (CNTs) and cellulose nanofibers (CNFs) reinforced shape memory polyurethane (PU) composite fibers and films have been fabricated via extrusion and casting methods. Cellulose nanofibers were obtained through acid hydrolysis of microcrystalline cellulose. This treatment aided in achieving stable suspensions of cellulose crystals in dimethylformamide (DMF), for subsequent incorporation into the shape memory matrix. CNTs were covalent functionalized with carboxyl groups (CNT‐COOH) and 4,4′‐methylenebis (phenylisocyanate) (MDI) (CNT‐MDI) to improve the dispersion efficiency between the CNT and the polyurethane. Significant improvement in tensile modulus and strength were achieved by incorporating both fillers up to 1 wt% without sacrificing the elongation at break. Electron microscopy was used to investigate the degree of dispersion and fracture surfaces of the composite fibers and films. The effects of the filler (type and concentration) on the degree of crystallinity and thermal properties of the hard and soft segments that form the PU sample were studied by calorimetry. Overall, results indicated that the homogeneous dispersion of nanotubes and cellulose throughout the PU matrix and the strong interfacial adhesion between nanotubes and/or cellulose and the matrix are responsible for the enhancement of mechanical and shape memory properties of the composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Finite strain 3D thermoviscoelastic constitutive model for shape memory polymers

A 3D thermoviscoelastic model is proposed to represent the thermomechanical behavior of shape memory polymers. The model is based on a physical understanding of the material behavior and a mechanical interpretation of the stress–strain–temperature changes observed during thermomechanical loading. The model is thermodynamically motivated and is formulated in a finite strain framework in order to account for large strain deformations. Model predictions capture critical features of shape memory polymer deformation and, in some cases, provide very favorable comparisons with experimental results. POLYM. ENG. SCI. 46:486–492, 2006. © 2006 Society of Plastics Engineers.     

Thermal behavior of novel hybrid inorganic-organic phosphazene polymers

The thermal behavior of the following systems have been investigated by TGA and XPS: the homopolymer of N:P:Cl₄(CH₂)(CH₂C₆H₄CH–CH₂) (1). copolymers of1 with MMA and styrene, and copolymers of N:P:Cl₄(1-C₃II) [C[OC(O)CH₃]–CH₃] (2) with MMA and styrene. Upon heating under TGA conditions the highest char yield (64wt⁰ ₀) is found for the homopolymer of1. The char yields for the copolymers appear to increase with increasing amounts of phosphazene incorporated. The one-step weight loss observed for the homopolymer of1 can be ascribed mainly to climination of HCl. The1 styrene copolymers decompose in one step, indicating that HCl elimination, ring degradation, and depolymerization take place simultaneously. The1 MMA copolymers show a two-step degradation. From XPS scans it follows that complete loss of chlorine takes place in the first step and probably in combination with some depolymerization of MMA units. In the second step phosphazene ring degradation is observed, accompanied by further carbonization of the sample. The2 styrene copolymers start to decompose about 100 C lowe than the1 MMA copolymers, also exhibiting a two-step TGA curve. The first step can be associated with breakdown of polymer chains at the C–C linkage between inorganic monomers. In the second step depolymerization of the styrene sequences. HCl elimination, and ring degradation occur.     

A novel approach to predict the recovery time of shape memory polymers

In this paper a novel approach is presented for prediction of the recovery time for a shape memory polymer. The Transient Stress Dip Tests of Fotheringham and Cherry are used to determine the two parameters of a Kelvin-Voigt element. The characteristic retardation time of this element can then be calculated to predict the recovery time. It is shown that this approach is successful in predicting the recovery times for a shape memory polymer drawn and recovered under a range of temperatures. Furthermore it is shown that the ratio of the recovery stress to the draw stress is independent of the drawing conditions to a very good approximation.     

High transition temperature shape memory polymers (SMPs) by telechelic oligomer approach

This work describes the synthesis and comparative shape memory properties of cross-linked networks derived from epoxy and cyanate ester monomers containing polyether oligomers as reactive shape memory segments. The hydroxy telechelic oligomers viz. polyethyleneglycol (PEG), polypropyleneglycol (PPG), and polytetramethyleneglycol (PTG) are reacted with epoxy–cyanate ester matrix resulting in shape memory polymers with high transition temperatures. The soft oligomer segments act as flexible linker unit which interconnect oxazolidone, isocyanurate and triazine ring structures in the cross-linked polymer. The resultant cyclomatrix SMPs exhibit high transition temperatures 132, 178 and 161 °C respectively for PEG, PPG and PTG integrated SMPs. The E_g/E_r ratios are increased in the order PEG < PTG < PPG. The PTG and PPG based SMPs show shape retention of 99% and shape recovery of >98% with recovery time <100 s. All the SMPs display good thermal stabilities (both inert and oxidative) above 275 °C.     

Preparation,shape memory properties and application research of PLA/PCL-based shape memory polymers doped with Al2O3 and lignin

In this paper, the influence of different material trademarks, mass ratios, the melt mass-flow rate (MMFR) and molecular weights (MW), mold and injection temperatures, Al₂O₃ powder and lignin on the shape memory properties of PLA/PCL SMP material (PPSM) were then analyzed in detail by different characteristic methods. Besides, three promising applications (Origami metamaterials and variable-stiffness grippers) are provided utilizing the PPSM doped with Al₂O₃/lignin. Eventually, a compensating strategy was discussed to improve the final configuration of the SMP after multi-cycles. The shape memory recovery ratios could be improved by increasing the MMFR of PLA and the MW of PCL. The addition of 2 g-Al₂O₃ could shorten the recovery time, while the addition of 2 g-lignin could increase the thermal-recovery force and mechanical performance. The shape memory rate under 20 g weights, initial peak forces at room and high temperatures of the origami metamaterials could reach 57%, 2027.29 N and 17.49 N, respectively. The tensile force of banding rebars could reach 150.29 N, which is promising to apply into the construction field.     

Improved oxidative biostability of porous shape memory polymers by substituting triethanolamine for glycerol

While many aromatic polyurethane systems suffer from poor hydrolytic stability, more recently proposed aliphatic systems are oxidatively labile. The use of the renewable monomer glycerol as a more oxidatively resistant moiety for inclusion in shape memory polymers (SMPs) is demonstrated here. Glycerol-containing SMPs and the amino alcohol control compositions are compared, with accelerated degradation testing displaying increased stability (time to complete mass loss) as a result of the inclusion of glycerol without sacrificing the shape memory, thermal transitions, or the ultralow density achieved with the control compositions. Gravimetric analysis in accelerated oxidative solution indicates that the control will undergo complete mass loss by approximately 18 days, while lower concentrations of glycerol will degrade fully by 30 days and higher concentrations will possess approximately 40% mass at the same time. In real-time degradation analysis, high concentrations of glycerol SMPs have 96% mass remaining at 8 months with 88% gel fraction remaining that that time, compared to less than 50% mass for the control samples with 5% gelation. Mechanically, low glycerol-containing SMPs were not robust enough for testing at three months, while high glycerol concentrations displayed increased elastic moduli (133% of virgin materials) and 18% decreased strain to failure. The role of the secondary alcohol, as well as isocyanates, is presented as being a crucial component in controlling degradation; a free secondary alcohol can more rapidly undergo oxidation or dehydration to ultimately yield carboxylic acids, aldehydes, carbon dioxide, and alkenes. Understanding these pathways will improve the utility of medical devices through more precise control of property loss and patient risk management through reduced degradation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47857.     

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     

Thermal behavior and shape memory properties of PCL blends film with PVC and PMMA polymers

Iranian Polymer Journal - Shape memory polymers have attracted extensive attention attributable to their characteristics and abundant applications. In this study, shape memory behavior and...     

Synthesis and characterization of high temperature cyanate-based shape memory polymers with functional polybutadiene/acrylonitrile

New thermosetting shape memory cyanate polymers (SMCPs) modified with polybutadiene/acrylonitrile (PBAN) were synthesized and compared with polyethylene glycol (PEG)-modified SMCPs for integration into the family of high temperature shape memory polymers with controllable glass transition temperatures (T_g) used in the aerospace industry. The materials were characterized in terms of microstructure, thermal properties, mechanical properties and shape memory properties by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile tests. Differing from the SMCP with PEG, the new cyanate-based shape memory polymer with PBAN (T_g ∼255.1.0 °C) had better shape memory properties and higher thermal stability (relatively high initial degradation temperature and high char residue value at 800 °C). Both of the SMCPs with PBAN and PEG displayed exceedingly high glass transition temperatures over 241.3 °C and higher toughness than unmodified polycyanurate. These qualities render them desirable candidates as matrices in polymer composites, particularly for space applications.     

From the synthesis and characterization of methacrylated fatty acid based precursors to shape memory polymers

Fatty acid based precursors were synthesized by a one‐step reaction from oleic or lauric acids and glycidyl methacrylate to be used later in polymer formulations. Different times of reaction, amounts of catalyst and initial ratios of reactants were evaluated, obtaining conversions higher than 0.9 for the best conditions. The monomers obtained are interesting alternatives to synthetics since they combine low cost with environmental advantages (i.e. higher bio‐carbon content). These polymeric precursors were reacted separately in cationic and free radical polymerizations with styrene (50 wt%) to evaluate their potential as greener monomers. The lauric acid precursor and free radical polymerization were the alternatives that produced elastomeric materials with higher glass transition temperatures and storage moduli. These results were related to the lesser plasticizing effect of the shorter fatty acid chain, in comparison with that of the oleic acid based monomer, and to a lower free volume in the formed structure during curing. Moreover, all the obtained polymers exhibited shape memory properties that can be activated by temperature changes. © 2018 Society of Chemical Industry     

Challenges of shape memory polymers: A review of the progress toward overcoming SMP's limitations

Many applications ranging from biomedical to aerospace have been proposed for the use of shape memory polymers (SMPs). To optimize SMPs properties for appropriately targeting such wide‐spreading application requirements, it becomes necessary to understand the structure/property relationships in SMPs. The literature was reviewed and the recent advances made in the development of SMPs were determined to establish guidelines for composition and structure considerations for designing SMPs with targeted chemical, physical, and shape memory (SM) properties. It was concluded that covalently crosslinked glassy thermosets appear to be better SMP candidates because of their intrinsically higher modulus, greater thermal and chemical stability, higher shape fixity and recovery, and possibly their longer cycle life. However, material design allows for reaching comparable or better properties for all classes of SMPs. This emphasizes that optimization of SMPs requires application‐specific molecular, structural, and geometrical design. Current techniques for improving stress recovery and cycle time, which compared to shape memory alloys are the two main limitations of SMPs, are extensively discussed. Understanding the relationships between the composition and structure of an SMP and its SM properties as well as its limitations enables one to better define the development areas for high performance SMPs. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Sustainable shape memory polymers based on epoxidized natural rubber cured by zinc ferulate via oxa-Michael reaction

Although various shape memory polymers (SMPs) or diverse applications have been widely reported, the SMPs based on rubbers have been rarely realized due to the low triggering temperature of rubbers. In another aspect, the SMPs based on sustainable substances are highly desired for the growing shortage in fossil resources. In the present study, we accordingly developed the sustainable SMPs with tunable triggering temperature, based on natural rubber (NR) and ferulic acid (FA) as the raw materials. Specifically, the SMPs are based on a crosslinked network of epoxidized natural rubber (ENR) crosslinked by in situ formed zinc ferulate (ZDF) via oxa-Michael reaction. The excellent shape memory effect (SME) is found in these SMPs, as evidenced by the high fixity/recovery ratio and the tunable triggering temperature. With the incorporation of natural halloysite nanotubes (HNTs), the stress and recovery rate of the SMPs are found to be tunable, which widens the application of this kind of SMPs. The combination of adoption of sustainable raw materials, and the excellent and tunable SME makes these SMPs potentially useful in many applications, such as various actuators and heat-shrinkable package materials.