Ultra low density and highly crosslinked biocompatible shape memory polyurethane foams

We report the development of highly chemically crosslinked, ultra low density (～0.015 g/cc) polyurethane shape memory foams synthesized from symmetrical, low molecular weight, and branched hydroxyl monomers. Sharp single glass transitions (T_g) customizable in the functional range of 45–70 °C were achieved. Thermomechanical testing confirmed shape memory behavior with 97–98% shape recovery over repeated cycles, a glassy storage modulus of 200–300 kPa, and recovery stresses of 5–15 kPa. Shape holding tests under constrained storage above the T_g showed stable shape memory. A high volume expansion of up to 70 times was seen on actuation of these foams from a fully compressed state. Low in vitro cell activation induced by the foam compared with controls demonstrates low acute bio‐reactivity. We believe these porous polymeric scaffolds constitute an important class of novel smart biomaterials with multiple potential applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Two-way shape memory behavior of styrene-based bilayer shape memory polymer plate

In this work, a bilayer shape memory polymer (SMP) composite plate with two-way shape memory behavior is simulated, in which two types of styrene-based SMPs with well-separated glass transition temperatures are assembled in parallel. The finite element (FE) software ABAQUS is selected to exhibit the two-way shape memory effect during the shape recovery step and the Generalized Maxwell Model with the WLF equation is applied to characterize the temperature-dependent properties of the SMP bilayer plates. The effect factors of axial predeformation, thermal expansion coefficient and plate thickness are all considered for the two-way shape memory behavior of the styrene-based bilayer SMP plate. After that, a smart gripper composed of four SMP composite plates is proposed to realize grabbing and releasing functions for one-step and staged heating recovery. The FE results provide some necessary theoretical guidelines for future soft smart structural designs and optimization.     

Investigation into stress recovery behavior of shape memory polyurethane fiber

In this work, the stress recovery behavior of shape memory polyurethane (SMPU) fiber was investigated. The as‐spun SMPU fibers were subjected to various programing‐recovery conditions. It was observed that recovering at 100 °C generated higher recovery stress than recovering at 150 °C. It was also found that, while hot‐drawn programed fiber has higher recovery stress than cold‐drawn programed fiber if recovered at 100 °C, cold‐drawn programed fiber has higher stabilized recovery stress than hot‐drawn programed counterpart when recovered at 150 °C. A morphological model was proposed based on the results from differential scanning calorimetry, Fourier transform infrared spectrometry, and X‐ray diffraction to understand the physics behind the different stress recovery behaviors. It is found that SMPU experiences different phase transitions and phase separations under different programing and stress recovery conditions. It is concluded that the two sequential phase separations taking place at 100 and 150 °C are primarily responsible for the differences in the stress recovery behavior. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1429–1440     

A hydrogel‐forming liquid crystalline elastomer exhibiting soft shape memory

Research in the field of liquid crystalline polymers has recently witnessed the introduction of liquid crystalline hydrogels. Here, we report the synthesis and characterization of a new liquid crystalline network featuring elastomeric softness, water‐swelling and shape memory characteristics. By comparing with a nonmesogenic network prepared using the same procedure, we reveal structure–property relationships of the liquid crystalline and crystalline polymer networks. Wide angle and small angle X‐ray scattering studies were used to examine the liquid crystalline ordering in both dry and hydrated states. Such ordering was found to be related to the observed shape memory and actuation (two‐way shape memory) properties and these phenomena are highlighted with demonstrations of shape change in response to heat and water stimuli. This study provides insight into the mechanisms affecting the shape evolution of water activated anisotropic liquid crystalline hydrogels and enables the future design of materials or devices for a variety of applications such as biomaterials interacting with body fluids in a hydrated state. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 38–52     

Bio‐based hyperbranched polyurethane/Fe3O4 nanocomposites as shape memory materials

The bio‐based shape memory polymers have generated immense interest as advanced smart materials. Mesua ferrea L. seed oil‐based hyperbranched polyurethane (HBPU)/Fe₃O₄ nanocomposites were prepared by the in‐situ polymerization technique. The transmission electron microscopy confirmed the homogeneous distribution of the Fe₃O₄ nanoparticles in polymer matrix, whereas Fourier transform infrared spectroscopic study revealed the presence of strong interfacial interactions between them. The incorporation of Fe₃O₄ (0 to 10 wt%) into the HBPU resulted in an increase in tensile strength (5.5–15 MPa) and scratch resistance (3–6 kg). The thermo‐gravimetric analysis indicated the improvement of thermal stability (240–270°C) of the nanocomposites. The nanocomposites exhibited full shape fixity, as well as almost full shape recovery under the microwave stimulus. The shape recovery speed increased with the increase of Fe₃O₄ nanoparticles content in the nanocomposites. Thus, the studied nanocomposites might be used as advanced shape memory materials in different potential fields. Copyright © 2013 John Wiley & Sons, Ltd.     

A unified modeling approach for amorphous shape memory polymers and shape memory polymer based syntactic foam

Shape memory polymers (SMPs) and shape memory polymer composites have drawn considerable attention in recent years for their shape memory effects. A unified modeling approach is proposed to describe thermomechanical behaviors and shape memory effects of thermally activated amorphous SMPs and SMP‐based syntactic foam by using the generalized finite deformation multiple relaxation viscoelastic theory coupled with time–temperature superposition property. In this paper, the thermoviscoelastic parameters are determined from a single dynamic mechanical analysis temperature sweep at a constant frequency. The relaxation time strongly depends on the temperature and the variation follows the time–temperature superposition principle. The horizontal shift factor can be obtained by the Williams–Landel–Ferry equation at temperatures above or close to the reference temperature (T_r), and by the Arrhenius equation at temperatures below T_r. As the Arruda–Boyce eight‐chain model captures the hyperelastic behavior of the material up to large deformation, it is used here to describe partial material behaviors. The thermal expansion coefficient of the material is regarded as temperature dependent. Comparisons between the model results and the thermomechanical experiments presented in the literature show an acceptable agreement. Copyright © 2016 John Wiley & Sons, Ltd.     

Impact of poly(ɛ‐caprolactone) architecture on the thermomechanical and shape memory properties

We report the synthesis of linear‐ and brush‐type poly(?‐caprolactone) (PCL) networks and investigate their thermal, mechanical, and shape memory behavior. Brush‐PCLs are prepared by ring‐opening metathesis polymerization (ROMP) of a norbornenyl‐functionalized ?‐caprolactone macromonomer (MM‐PCL) of different molecular weights. The linear analog, diacrylate end‐functionalized PCL (linear‐PCL), having comparable molecular weight of side chain of brush‐PCL is also synthesized. These polymers are thermally cured by a radical initiator in the presence of poly(ethylene glycol) diacrylate crosslinker. Thermal and linear viscoelastic properties as well as shape memory performance of the resulting PCL networks are investigated, and are significantly impacted by the PCL architecture. Therefore, our work highlights that tailoring macromolecular architecture is useful strategy to manipulate thermal, mechanical, and resulting shape memory properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3424–3433     

Effect of thermal expansion on shape memory behavior of polyurethane and its nanocomposites

The effects of thermal expansion on shape memory performance of shape memory polyurethanes and their nanocomposites with organoclay, carbon nanofiber (CNF), silicon carbide (SiC), and carbon black (CB) were evaluated. The shape memory test cycle involved tensile deformation at above the trigger temperature to initiate shape memory function, cooling to room temperature to fix the shape, and shape recovery induced by heating to above the trigger temperature. Phenomenological models were used to interpret the experimental data on coefficient of thermal expansion (CTE). It was found that Kerner model showed good fit for composites of SiC and CB, and Halpin model gave better fit for composites of organoclay and CNF. It was observed that thermal expansion exerts negative effect on recovered strain, the extent of which depends on the magnitude of temperature gradient, CTE, and the level of tensile strain. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1437–1449, 2008     

Thermo‐responsive shape memory behavior of poly(styrene‐b‐isoprene‐b‐styrene)/ethylene‐1‐octene copolymer thermoplastic elastomer blends

Thermally‐triggered shape memory polymers (SMPs) are smart materials, which are capable of changing their shapes when they are exposed a heat stimulant. Blending semi‐crystalline and elastomeric polymers is an easy and low‐cost way to obtain thermo‐responsive SMPs. In this work, novel poly(ethylene‐co‐1‐octene) (PEO) and poly(styrene‐b‐isoprene‐b‐styrene) (SIS) thermoplastic elastomer blends were prepared via melt blending method. The morphological, mechanical, rheological properties and shape memory behaviours of the blends were investigated in detail. In morphological analysis, co‐continuous morphology was found for 50 wt% PEO/50 wt% SIS and 60 wt% PEO/40 wt% SIS (60PEO/40SIS) blends. The shape memory analysis performing by dynamic mechanical analyzer showed that the 60PEO/40SIS blend also exhibited the optimum shape memory performance with 95.74% shape fixing and 98.98% shape recovery. Qualitatively shape memory analysis in hot‐water pointed out that the amount of semi‐crystalline PEO promotes shape fixing ability of the blends whereas SIS content enhances shape recovery capability. Although the SIS and PEO are immiscible polymers, the blends of them were exhibited good elastomeric properties with regard to tensile strength, toughness, and elongation at break.     

Waterborne polyurethane nanocomposites having shape memory effects

UV curable waterborne polyurethane/silica nanocomposites were designed and synthesized with functionalized silicas, where the functionalization was made with allyl isocyanate. The incorporated silica particles gave triple effects of multifunctional chemical cross‐links, reinforcing fillers, and stress relaxation retarders. Consequently, functionalized silica incorporated into the polymer chains showed significantly improved mechanical and thermal properties than the simple addition of unmodified silica. Notably, over 99% shape fixity and shape recovery with minimum cyclic hysteresis were obtained for the repeated cycles at 1% loading of the modified silica. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Predicting shape memory characteristics of polyurethane in three‐point bending deformation

As a kind of an exceptional material, the temperature‐responding shape memory polymer can fix a temporary shape when cooled down and recover to its original shape when reheated up. Several models have been developed to describe the process. In the present work, we use the generalized Maxwell model to predict the shape memory characteristics of polyurethane in three‐point bending deformation by means of three‐dimensional finite element simulation. The deformation–temperature–stress behavior is obtained numerically. The results reveal that under the condition of accelerating reheating rates at the stage of stress‐free recovery, the maximum recovery rate occurs at higher temperature whereas the recovery ratio decreases. When the deformation degree enlarges, the maximum recovery stress increases in the situation of constrained recovery. The micro‐motion theory of polymer segments is used to explain the characteristics in the shape memory cycle. The simulated results agree well with previous researches, which demonstrate that the simplified model and the numerical simulation method are helpful for both scientific research and engineering development about shape memory polymers. Copyright © 2014 John Wiley & Sons, Ltd.     

Organic‐montmorillonite modified shape memory epoxy composite

A series of organic‐montmorillonite (OMMT) modified shape memory epoxy (SMEP) composites were prepared for the purpose of application on space deployable structures. Tensile test, dynamic mechanical analysis (DMA), X‐ray diffraction (XRD), scanning electron microscope (SEM), and fold‐deploy shape memory test methods were used to characterize the mechanical, structure, and shape memory properties of these materials. The results showed addition of OMMT could improve the composites' toughness, tensile strength, transition temperature, and shape recovery speed, while shape recovery ratio was unaffected. Composite with 3wt%. OMMT had the optimum combination property. It could fully recover its original shape in about 2 min at 185°C under the maximum bending angle of 180°. Its elongation at break and tensile strength were increased by 835 and 17.4%, respectively, compared to that of neat SMEP. The transition temperature also slightly increased. Copyright © 2010 John Wiley & Sons, Ltd.     

Room temperature deformable shape memory composite with fine‐tuned crystallization induced via nanoclay particles

It is known that particular types of semi‐crystalline/elastomer polymer blends exhibit shape memory effects (SME) due to the dispersion of two immiscible phases. In this study, the crystal structure of polylactic acid (PLA)/ thermoplastic polyurethane (TPU) based shape memory polymer (SMP) is altered by incorporating small amounts of montmorillonite (MMT) nanoclay. The results indicate the incorporation of MMT can improve the compatibility of the two different polymers. Moreover, the presence of MMT affects the total crystallinity of the SMP and improves mechanical properties. Lastly, uniaxial stretching deformation can be applied to the SMP at room temperature conditions while maintaining its shape memory properties. With 1 wt % MMT particles, the recovery ratio (Rr) was nearly 95%, which indicated a strong recovery effect. The shape‐fixing ratio (Rf) remained above 95% for all composites due to plastic deformation applied at room temperature. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1197–1206     

Preparation of modified multi‐walled carbon nanotubes as a reinforcement for epoxy shape‐memory polymer composites

Effectively improving the mechanical properties and thermal resistance of epoxy shape‐memory polymers (ESMPs) without affecting their shape‐memory performance is necessary to expand these polymers in practical applications. In this article, modified multi‐walled carbon nanotubes (MWCNTs) were prepared and used as efficient reinforcement for enhancing the comprehensive properties of ESMPs. Increases of nearly 289% to 444% for impact strength and 112% to 184% for tensile force were obtained by adding only 0.1 to 1 wt% epoxy‐modified MWCNTs. The addition of unmodified and carboxyl‐modified MWCNTs was also investigated but showed less impact on the mechanical properties of the ESMPs than epoxy‐modified MWCNTs. Thermogravimetry analysis (TGA) and dynamic mechanical analyses (DMA) showed that less than 1 wt% modified MWCNTs can enhance the heat resistance of ESMPs greatly. Although the shape recovery time for composite materials increased upon adding the MWCNTs, the entire recovery time was still less than 1 minute, and the shape recovery rate was relatively high, nearly 100%.     

Actuation design for high‐performance shape memory polyurethanes

A series of shape memory polyurethanes were synthesized from poly(tetramethylene glycol), 4,4‐methylene diphenyl diisocyanate, and 1,3‐butanediol. The prepolymers with different molecular weights (M_c) were capped with 2‐hydroxyl ethylacrylate or 3‐aminopropyltriethoxysilane (APTES) and crosslinked by UV curing or a sol–gel reaction. Variations of the crosslinker functionality (f), subchain density (N), and hard segment content (HSC) produced systematic variations of the glass transition temperature (6–45 °C), accompanied by changes in the mechanical, dynamic mechanical and shape memory properties. More than 95% of shape fixity and 98% of shape recovery up to the fourth cycles were obtained with APTES crosslinked 3000M_c with 30% of HSC. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1473–1479     

A fully coupled thermo‐viscoelastic finite element model for self‐folding shape memory polymer sheets

The thermo‐mechanical response of heat activated shape memory polymers (SMPs) has been investigated using a thermo‐viscoelastic finite element analysis that accounts for external and internal heat sources. SMPs can be thermally stimulated by external heat sources, such as temperature and surface heat flux, or from internal viscous heating. Viscous heating can significantly affect the response of SMP sheets by increasing the temperature during pre‐strain, which accelerates stress relaxation. This stress relaxation results in a slower shrinking rate when the SMP is reheated. Viscous heating also causes an increase in temperatures during unconstrained recovery. The predicted results elucidate how the coupled thermo‐mechanical loading conditions affect folding and unfolding of SMP sheets in response to localized heating in a hinged region. A parametric study of sheet thickness, hinge width, degree of pre‐strain, and hinge surface temperature is also conducted. The validated results can provide guidelines for the design of functional, self‐folding structures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1207–1219     

Optimization of the shape memory effect in shape memory polymers

In this article, we show that given a thermoresponsive shape memory polymer, it is possible to alter a number of its properties, such as the recovery temperature, shape fixity ratio, maximum recovery stress, and final recovery stress (and even a right combination of some of them, e.g., the maximum recovery stress and final recovery stress), simply by means of selecting the programming temperature to achieve optimized performance. Some concerns for the implementation in real engineering practice are also discussed. Although the focus is on the case of a fixed maximum strain in programming, alternative programming approaches can be investigated in a similar way for optimized performance as well. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A novel shape memory poly(ε‐caprolactone) network via UV‐triggered thiol‐ene reaction

A facile method to prepare shape memory polymers crosslinked by SiO₂ is described. A series of biodegradable shape memory networks were obtained through thiol‐ene reaction triggered by UV irradiation between surface‐thiol‐modified SiO₂ nanoparticles and end‐acrylate poly (ε‐caprolactone) (PCL). The highly selective thiol‐ene reaction ensured a uniform distribution of PCL chains between crosslinkers, contributing well‐defined network architecture with enhanced mechanical and shape‐memory properties. Thiol‐functionalized silica nanoparticle was characterized by using FTIR and XPS analysis, and ¹H NMR spectra was used to confirm the successful modification of terminal hydroxyl group of PCL diol. Surface‐modified silica particles were found well dispersible in acrylate‐capped PCL supported by SEM. Thermal and crystalline behaviors of the obtained polymers were analyzed by DSC and XRD, and DMA measurement proved good mechanical property. The shape memory behavior and tensile strength was somewhat tunable by the length of PCL. Acceptably, sample SiO₂‐SMP2k presented 99% recovery ratio and 97% shape fixity, and its relatively high tensile strength showed an attractive potential for biomedical application. Finally, a possible molecular mechanism accounting for the shape memory property was illustrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 692–701     

Hydrogel‐like elastic membrane consisting of semi‐interpenetrating polymer networks based on a phosphorylcholine polymer and a segmented polyurethane

To obtain a hydrogel‐like elastic membrane, we prepared semi‐interpenetrating polymer networks (IPNs) by the radical polymerization of methacrylates such as 2‐methacryloyloxyethyl phosphorylcholine (MPC), 2‐hydroxyethylmethacrylate, and triethyleneglycol dimethacrylate diffused into segmented polyurethane (SPU) membranes swollen with a monomer mixture. The values of Young's modulus for the hydrated semi‐IPN membranes were less than that for an SPU membrane because of higher hydration, but they were much higher than that for a hydrated MPC polymer gel (non‐SPU). According to a thermal analysis, the MPC polymer influenced the segment association of SPU. The diffusion coefficient of 8‐anilino‐1‐naphthalenesulfonic acid sodium salt from the semi‐IPN membrane could be controlled with different MPC unit concentrations in the membrane, and it was about 7 × 10² times higher than that of the SPU membrane. Fibroblast cell adhesion on the semi‐IPN membrane was effectively reduced by the MPC units. We concluded that semi‐IPNs composed of the MPC polymer and SPU may be novel polymer materials possessing attractive mechanical, diffusive‐release, and nonbiofouling properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 68–75, 2003     

Two‐way multi‐shape memory properties of peroxide crosslinked ethylene vinyl‐acetate copolymer (EVA)/polycaprolactone (PCL) blends

Rare studies have investigated on the 2‐way shape memory crosslinked blends with multiple shape memory behavior up to date. To consider the merit of commercial cost‐competitive crystalline polymers, ethylene vinyl‐acetate copolymer (EVA) / polycaprolactone (PCL) blends (60/40 and 30/70) were peroxide‐cured to form the 2‐way multi‐shape memory crosslinked blends using a melt‐blending method. Both resins were selected to have a similar controlled crosslinking degree, which allowed us to distinctly evaluate their actuation contributions from the cooling‐induced elongation (crystallization) and from the entropy‐driven elongation during cooling process, respectively. In the 2‐way process for the 60/40 system, 2 respective peaks contributed from the cooling‐induced crystallization of EVA and PCL in the cooling curves based on the strain derivate rates at various temperatures were observed. After the cooling process under the loading stress of 150 kPa, the 2‐step heating‐induced contraction process with increasing temperature started at 54.1°C above the melting temperature of PCL at 52.3°C and EVA at 78.3°C, demonstrating 2‐way multi‐shape memory behavior. The multi‐step behavior was more prominent at higher PCL composition and higher load for the 30/70 system. It was found that the entropy‐driven contribution to the overall actuation magnitude increased with increasing nominal loads due to the increased orientation of molecular networks in the blends. The current approach offers numerous possibilities in preparing 2‐way multi‐shape memory crosslinked blends.