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     

High shape-memory effect of hindered phenol/nitrile–butadiene rubber composites by forming hydrogen bonding

To widen the type and scope of use of shape memory polymers (SMPs), we added hindered phenol (AO-80) to nitrile–butadiene rubber (NBR) to gain a group of AO-80/NBR rubber composites. The glass transition temperature (T_g), structure, mechanical properties, and shape memory properties of the AO-80/NBR rubber composites were characterized. It was concluded that the dispersion of AO-80 in the NBR matrix was homogeneous and intra-molecular hydrogen bonds were formed between the hydroxyl groups ( OH) of AO-80 and the cyano groups ( CN) of NBR molecular chain. The dosage of AO-80 added could be changed to tune the T_g. AO-80/NBR rubber composites revealed outstanding shape fixity and shape recovery. The method for tuning the T_g of AO-80/NBR rubber composites will provide an idea for the fabrication and design of new SMPs. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48911.     

Incorporating bis‐benzimidazole into polyimide chains for effectively improving thermal resistance and dimensional stability

Heteroaromatic 6,6′‐bis[2‐(4‐aminobenzene)benzimidazole] and its corresponding copolyimides were synthesized to produce high temperature resistant polyimides (PIs). Due to the rigidity and aromaticity of heterocyclic bis‐benzimidazole, and the increased hydrogen bonding interactions, these PIs were found to have a high glass transition temperature (T_g) over 457 °C, which also guarantees a better dimensional stability with a coefficient of thermal expansion (CTE) lower than 10 ppm K^?1 in a wider temperature range of 50–400 °C. In addition, the PIs exhibit excellent thermal stability (5% weight loss temperature higher than 559 °C) along with outstanding mechanical properties. This study demonstrates the viability to access PIs with ultrahigh T_g and low CTE in a wider range of temperature by the incorporation of bis‐benzimidazole moieties. © 2019 Society of Chemical Industry     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. v. shape memory effect

A series of new shape memory polymers are synthesized by the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), and/or conjugated LoSatSoy oil with styrene and divinylbenzene, norbornadiene, or dicyclopentadiene initiated by boron trifluoride diethyl etherate or related modified initiators. The shape memory properties of the soybean oil polymers are characterized by the deformability (D) of the materials at temperatures higher than their glass‐transition temperatures (T_g), the degree to which the deformation is subsequently fixed at ambient temperature (FD), and the final shape recovery (R) upon being reheated. It is found that a T_g well above ambient temperature and a stable crosslinked network are two prerequisites for these soybean oil polymers to exhibit shape memory effects. Good shape memory materials with high D, FD, and R values are prepared by controlling the crosslink densities and the rigidity of the polymer backbones. The advantage of the soybean oil polymers lies in the high degree of chemical control over the shape memory characteristics. This makes these materials particularly promising in applications where shape memory properties are desirable. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1533–1543, 2002; DOI 10.1002/app.10493     

Preparation and characterization of aromatic polyimides and related copolymers

Copolyimides containing BTDA-3DDS and BTDA-4ODA units have been synthesized by solution imidization methods. The copolyimides have high T_g's (267–283°C) and high decomposition temperatures (540–575°C; nitrogen); both properties are dependent on composition. Those copolymides with low concentrations of BTDA-4ODA are generally soluble in organic solvents, whereas those copolyimides with higher BTDA-4ODA content are only partially soluble or insoluble. However, all the copolyimides prepared can be compression molded. It has also been found that segmental motion above T_g is heavily suppressed in the BTDA-4ODA homopolymer relative to that in the BTDA-3DDS homopolymer. This reduction in molecular motion may severely hinder the solubility and fusibility of the BTDA-4ODA homopolymer. © 1993 John Wiley & Sons, Inc.     

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.     

Influences of phase composition and thermomechanical conditions on shape memory properties of segmented polyurethanes with amorphous reversible phase

We synthesized series of shape memory polyurethanes with amorphous reversible phase (T_g‐SMPUs) and systematically studied their microphase structure and shape memory properties. The T_g‐SMPUs having no or less hard phase showed lower shape recovery. When the volume fraction of hard phase was in the range of 20–30%, the T_g‐SMPUs exhibited the highest shape recovery. As the fraction of hard phase increased further the shape recovery decreased, because more polymer components with higher glass transition temperatures (T_gs) would participate in strain storage. For the T_g‐SMPUs having similar T_gs, those polymers having higher volume fraction of hard phase exhibited higher shape fixity, broader shape recovery region, and larger recovery stress. Increasing deformation strain could raise shape fixity and recovery stress but broaden shape recovery region. The highest recovery stress of a material could be achieved when the deformation occurred at its glass transition temperature below which decreasing deformation temperature could not increase recovery stress further. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Syntheses and properties of polyimides derived from diamines containing 2,5‐disubstituted pyridine group

A series of novel homo‐ and copolyimides containing pyridine units were prepared from the heteroaromatic diamines, 2,5‐bis (4‐aminophenyl) pyridine and 2‐(4‐aminophenyl)‐5‐aminopyridine, with pyromelltic dianhydride (PMDA), and 3,3′, 4,4′‐biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two‐step thermal imidizaton method. The poly(amic acid) precursors have inherent viscosities of 1.60–9.64 dL/g (c = 0.5 g/dL in DMAC, 30°C) and all of them can be cast and thermally converted into flexible and tough polyimide films. All of the polyimides show excellent thermal stability and mechanical properties. The polyimides have 10% weight loss temperature in the range of 548–598°C in air. The glass transition temperatures of the PMDA‐based samples are in the range of 395–438°C, while the BPDA‐based polyimides show two glass transition temperatures (T_g1 and T_g2), ranging from 268 to 353°C and from 395 to 418°C, respectively. The flexible films possess tensile modulus in the range of 3.42–6.39 GPa, strength in the range of 112–363 MPa and an elongation at break in the range of 1.2–69%. The strong reflection peaks in the wide‐angle X‐ray diffraction patterns indicate that the polyimides have a high packing density and crystallinity. The polymer films are insoluble in common organic solvents exhibiting high chemical resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1844–1851, 2006     

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.     

Synthesis and characterization of benzimidazole‐based low CTE block copolyimides

A series of block and random copolyimide films were synthesized from various molar ratios of two diamines, rigid 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (APBI) and flexible 4,4′‐oxydianiline (ODA) by polycondensation with dianhydride 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The contents of APBI ranged from 10 to 60 mol % in copolyimides. The copolyimide films obtained by thermal imidization of poly(amic acid) solutions, were characterized by TMA, DMA, TGA, DSC, wide‐angle X‐ray diffraction, FTIR, tensile testing, water uptake (WU), and dielectric constant measurements. Rigid heterocyclic diamine APBI with interchain hydrogen bonding capability, led to low coefficient of thermal expansion (CTE), high T_g, high thermal stability and better mechanical properties. Increasing the APBI mol % caused a gradual decrease in the CTE and increase in T_g, thermal stability and tensile strength properties of the copolyimides films. Moreover, significantly enhanced thermal and mechanical properties of the block copolyimides were also found as compared to random copolyimides. The block copolyimide with APBI content of 60 mol %, achieved excellent properties, that is, a low CTE (4.7 ppm/K), a high T_g at 377°C, 5% weight loss at 562°C and a tensile strength at 198 MPa. This can be interpreted because of comparatively higher degree of molecular orientation in block copolyimides. These copolyimides also exhibited better dielectric constant and WU. This combination of properties makes them attractive candidates for base film materials in future microelectronics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal,mechanical, and shape‐memory properties of nanorubber‐toughened,epoxy‐based shape‐memory nanocomposites

Epoxy‐based shape‐memory polymers (ESMPs) are a type of the most promising engineering smart polymers. However, their inherent brittleness limits their applications. Existing modification approaches are either based on complicated chemical reactions or done at the cost of the thermal properties of the ESMPs. In this study, a simple approach was used to fabricate ESMPs with the aim of improving their overall properties by introducing crosslinked carboxylic nitrile–butadiene nanorubber (CNBNR) into the ESMP network. The results show that the toughness of the CNBNR–ESMP nanocomposites greatly improved at both room temperature and the glass‐transition temperature (T_g) over that of the pure ESMP. Meanwhile, the increase in the toughness did not negatively affect other macroscopic properties. The CNBNR–ESMP nanocomposites presented improved thermal properties with a T_g in a stable range around 100 °C, enhanced thermal stabilities, and superior shape‐memory performance in terms of the shape‐fixing ratio, shape‐recovery ratio, shape‐recovery time, and repeatability of shape‐memory cycles. The combined property improvements and the simplicity of the manufacturing process demonstrated that the CNBNR–ESMP nanocomposites are desirable candidates for large‐scale applications in the engineering field as smart structural materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45780.     

Molecular simulation of the glass transition and proton conductivity of 2,2′‐benzidinedisulfonic acid and 4,4′‐diaminodiphenylether‐2,2′‐disulfonic acid‐based copolyimides as polyelectrolytes for fuel cell applications

The glass transition temperatures (T_gs) and proton conductivities of polyimides synthesized from naphthalene‐1,4,5,8‐tetracarboxylic dianhydride (NTDA), 2,2′‐benzidinedisulfonic acid (BDSA), 4,4′‐diaminodiphenylether‐2,2′‐disulfonic acid (ODADS), and non‐sulfonated diamine monomers have been predicted using molecular dynamics simulations. The specific volumes for two dry and four hydrated NTDA‐based polyimides were plotted versus temperatures above and below T_gs to obtain the glass transition temperatures. The simulation results suggest that the ODADS‐based polyimide membranes exhibit lower T_gs and thus better mechanical properties than the BDSA‐based polyimides, which may be attributed to the high mobility of backbones of ODADS as supported by the vectorial autocorrelation function (VACF) results of this study. In addition, comparison of the simulated T_gs for the dry and hydrated ODADS‐based polyimides has shown that water content in polyimides can affect their T_gs. The proton conductivities of a representative polyimide in both dry and hydrated conditions have been obtained from molecular dynamics simulations of the proton and hydronium ion diffusion. The simulated conductivity for the hydrated NTDA‐ODADS/BAPB cell is in reasonable agreement with the experimental value obtained from the AC impedance method. The relationship between the chemical composition, chain flexibility, and the glass transition and proton conduction of these NTDA‐based polyimides was explored on the basis of VACF and pair correlation function analysis. Copyright © 2006 Society of Chemical Industry     

Shape‐memory polymer networks with Fe3O4 nanoparticles for remote activation

Shape‐memory polymers (SMPs) have recently shown the capacity to actuate by remote heating via the incorporation of magnetic nanoparticles into the polymer matrix and exposure to an alternating magnetic field. In this study, methacrylate‐based thermoset SMP networks were synthesized through free‐radical polymerization with varying amounts of Fe₃O₄ magnetite (0, 1, and 2.5 wt %). Furthermore, the chemistry of the networks was controlled to maintain a constant glass transition temperature (T_g) while varying the degree of chemical crosslinking. Remote heating of the networks was shown to be a direct function of the nanoparticle concentration and independent of the chemistry. Magnetite reinforcement was shown to influence the thermomechanical properties of the networks; increasing Fe₃O₄ concentrations led to decreases in T_g and rubbery modulus. However, networks with a higher degree of crosslinking were more resistant to thermomechanical changes with respect to magnetite concentration. Strain to failure was shown to decrease with the addition of nanoparticles and the free‐strain shape‐memory cycle was investigated for all of the networks. Networks with lower degrees of crosslinking and high magnetite concentrations showed a significant amount of irrecoverable strain. Last, the use of remotely heated shape‐memory materials is discussed in light of potential biomedical applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of monomer composition on properties of copolyimides derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐oxydianiline/1,3‐bis (4‐aminophenoxy)benzene

A series of uncontrolled molecular weight homopolyimides and copolyimides based on 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA)/4,4′‐oxydianiline (4,4′‐ODA)/1,3‐bis(4‐aminophenoxy)benzene (TPER) were synthesized. All the polyimides displayed excellent thermal stability and mechanical properties, as evidenced by dynamic thermogravimetric analysis and tensile properties testing. A singular glass transition temperature (T_g) was found for each composite from either differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), but the values determined from tan δ of DMA were much different from those determined from DSC and storage modulus (E′) of DMA. The Fox equation was used to estimate the random T_g values. Some composites exhibited re‐crystallization after quenching from the melt; upon heating, multi‐melting behavior was observed after isothermal crystallization at different temperatures. The equilibrium melting temperature was estimated using the Hoffman‐Weeks method. Additionally, DMA was conducted to obtain E′ and tan δ. Optical properties were strongly dependent on the monomer composition as evidenced by UV‐visible spectra. X‐ray diffraction was used to interpret the crystal structure. All the results indicated that composites with TPER composition ≥ 70% were dominated by the TPER/s‐BPDA polyimide phase, and ≤40% by the 4,4′‐ODA/s‐BPDA polyimide phase. When the ratio between the two diamines was close to 1:1, the properties of the copolyimides were very irregular, which means a complicated internal structure. Copyright © 2011 Society of Chemical Industry     

Dynamic mechanical and shape memory properties of copolymers based on o‐allylphenol type benzoxazines and diglycidyl ether of bisphenol‐A

Three benzoxazines based on o‐allylphenol and 1,6‐hexamethylenediamine (HDA) or 4,4′‐diaminodiphenyl methane (DDM) or 4,4′‐diaminodiphenyl ether (DDE) were respectively blended with diglycidyl ether of bisphenol‐A (DGEBA) in various weight ratios followed by thermal polymerization to prepare three series of benzoxazine/DGEBA copolymers. With increasing DGEBA content, the peak temperature of the exothermic peaks in the DSC curves shows a systematic increase for the three series of benzoxazine/DGEBA blends. Each copolymer shows a single glass transition temperature (T_g). As the content of DGEBA is increased, T_g reaches a minimum for the copolymer system based on HDA but a maximum for the two systems based on DDM and DDE. For the same benzoxazine/DGEBA weight ratio, copolymers based on DDM and DDE show high T_g values over those based on HDA. The three series of benzoxazine/DGEBA copolymers exhibit a one‐way dual shape memory effect based on T_g, and the shape memory properties of the copolymers under tensile deformation mode vary with the variation of both diamine bridge structure and DGEBA content. © 2018 Society of Chemical Industry     

Effect of molecular structures on polyimide properties: Comparison between estimations and experiments

The density and glass transition temperature (T_g) of 11 polyimides were investigated by experiments and predictions using the connectivity indices method to explore the structure–property relationships. The predicted results are in good agreement with the experimental data. The mean interchain spacings (d‐spacings) of polyimides increase with the introduction of bridging groups, i.e., following the order: PDA < BZD < ODA < MDA < BDAF, while the densities increase in the order of MDA < BZD < PDA, and cohesive energy densities (CEDs) of polyimides change following the order of BDAF < MDA < ODA < BZD < PDA. In addition, the glass transition temperatures (T_g's) increase as the CEDs increase for the polyimides prepared from the same dianhydride and different diamines, whereas no certain correlation exists between T_g's and the values of the characteristic ratio (C_∞). This indicates that the strength of interchain interaction influences the T_g's of polyimides much stronger than the chain flexibility. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 998–1003, 2007     

Tailoring new bisphenol a ethoxylated shape memory polyurethanes

Shape memory polyurethanes (SMPUs) have generated great attention because of their unique properties. These properties are result of a particular molecular structure consisting of flexible molecular chains with low glass transition temperatures alternating with hard urethane segments. In this field, bisphenol A (BA) has been used for a long time as chain extender due to the good properties of the obtained SPMU materials. Nevertheless, the high toxicity of this compound has caused a high decrease on its use. For this reason, it has been selected a lower toxicity compound, bisphenol A ethoxylate (BAE). In this work, it is described a new SMPUs based on BAE and the influence of the hard segment on the thermo-mechanical properties and shape memory capacity. For that, both the proportion of the components and the diisocyanate employed (2,4-toluene diisocyanate (TDI), 4,4′-methylene bis(phenylisocyanate) (MDI) or a TDI/MDI mixture) have been modified. Then, depending on the molecular architecture achieved, the polyurethanes present different properties, which were studied by different techniques, such as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic-mechanical thermal analysis (DMTA). It has been observed that glass transition temperature (T_g) increases as the hard phase content in the PU samples increases. In addition, T_g-MDI > T_g-MDI-TDI > T_g-TDI, so it is possible to control the T_g of the material, that is, shape memory transition temperature varying the diisocyanate. Finally, the shape memory capacity of the PUs was evaluated by thermo-mechanical analysis (TMA). All the synthesized PUs have shown good shape memory effect with fixation ratios up to 80% and recovery ratios close to 100%.     

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     

Effect of molecular weight on shape memory behavior in polyurethane films

Understanding the relationship between the number‐average molecular weight (M_n) and the shape memory behavior of polymers is crucial for a complete picture of their thermomechanical properties, and hence for the development of smart materials, and, in particular, in textile technology. We report here on the study of shape memory properties as a function of M_n of polymers. Shape memory polyurethanes (SMPUs) of different M_n were synthesized, with various catalyst contents or molar ratio(r = NCO/OH) in the composition. In particular, two types of SMPU, namely T_m and T_g types according to their switch temperature type, were synthesized to compare the influence of M_n on their shape memory behavior. X‐ray diffraction, differential scanning calorimetry, dynamic mechanical analysis, and shape memory behavior results for the SMPUs are presented. The results indicate that the melting temperature (T_m), the glass transition temperature (T_g), the crystallinity, and the crystallizability of the soft segment in SMPUs are influenced significantly by M_n, before reaching a critical limit around 200 000 g mol^?1. Characterization of the shape memory effect in PU films suggests that the T_m‐type films generally show higher shape fixities than the T_g‐type films. In addition, this shape fixity decreases with increasing M_n in the T_g‐type SMPU, but the shape recovery increases with M_n in both types of SMPU. The shape recovery temperature, in contrast, decreases with M_n as suggested by the result of their thermal strain recovery. It is concluded that a higher molecular weight (M_n > 200 000 g mol^?1) is a prerequisite for SMPUs to exhibit higher shape recovery at a particular temperature. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of copolyimides with high solubility

A series of copolyimides were prepared from various diamines (polysiloxane and isophorone units) with aromatic tetracarboxylic dianhydrides via a two‐step (thermal imidization) method. The monomers and polymers were produced in high yields, and the copolyimides containing Si? O? C bonds and asymmetric meta catenation in the polymer backbone exhibited good solubility. The glass‐transition temperatures (T_g's) of all the copolyimides were found to be 201–262 and 215–258°C by differential scanning calorimetry (DSC) and dynamic mechanical analysis, respectively. Thermogravimetric analyses indicated that the polymers were fairly stable up to 502–578°C (10 wt % loss in N2) and 490–574°C (10 wt % loss in air). The char yields at 800°C in N2 and air atmospheres were 26–59 and 20–53%, respectively. The copolymerization results, determined with 1H‐NMR and DSC, indicated a random copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1963–1970, 2003