Microstructural and mechanical property evolutions of shape memory polyurethane during a thermodynamic cycle

To better understand the shape memory behaviors of synthesized shape memory polyurethane (SMPU) sealant with a tailored transition temperature (T_t) for concrete pavement joints, the thermal and dynamic mechanical properties of SMPU were first characterized to determine the shape memory switching temperature of SMPU. Then the microstructural and mechanical property evolutions of SMPU in the original, programmed, and recovered states during a five‐step thermodynamic cycle were discussed, respectively. The results indicate that the tailored T_t of prepared SMPU can be used as the shape memory switching temperature to match its working temperature. Further, the programming causes the phase separation in SMPU, leading to an obvious anisotropy. The SMPU has satisfactory shape memory performance. The orientation of molecular chains in soft segments is confirmed along the stretching direction. The oriented molecular chains can restore to the naturally curled state during the free recovery. Finally, the programming improves the mechanical properties of SMPU. The recovered SMPU shows a slight decrease in mechanical properties because of the partially impaired crystal structures and broken molecular segments during the programming and recovery. It is concluded that the synthesized SMPU with the specially tailored T_t is suitable to use as a sealant of concrete pavement joints. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45703.     

Poly(dl‐Lactic Acid)‐Based Linear Polyurethanes Capable of Forming Physical Crosslinking via UPy Quadruple Hydrogen Bonding Assembly

Linear shape memory polyurethanes based on poly(dl ‐lactic acid) (PDLLA) macrodiol (PDLLA‐SMPUs) have various advantages such as good processability, biodegradability, shape memory effect, and biocompatibility, yet the insufficient mechanical properties prevent their effective applications in bone repair. 2‐Ureido‐4[1H]‐pyrimidone (UPy) can form strong quadruple hydrogen bonding. Here, a new linear PDLLA‐SMPU containing pendant UPy units (UPy‐p‐PDLLA‐SMPU) is designed and synthesized. The pendant UPy units may dimerize to form physical crosslinking among UPy‐p‐PDLLA‐SMPU chains. As a result, UPy‐p‐PDLLA‐SMPU demonstrates both good processability and significantly higher mechanical properties than the corresponding linear PDLLA‐SMPU without pendant UPys. In addition, UPy‐p‐PDLLA‐SMPU shows excellent shape memory effect near body temperature, with a shape fixity ratio of up to 98.6% and a recovery ratio of up to 92.9%. This work provides a new strategy to design SMPUs integrating the merits of linear and crosslinked polyurethanes, and the obtained UPy‐p‐PDLLA‐SMPU is a promising material for bone tissue repair in view of the mechanical, thermal, and shape memory properties.     

Dependency of the shape memory properties of a polyurethane upon thermomechanical cyclic conditions

The relationship between the shape memory properties and thermomechanical cyclic conditions was investigated with a type of shape memory polyurethane (SMPU). The thermal and dynamic mechanical properties of the polyurethane were examined by using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). It was found that the SMPU exhibited good shape memory effects (SMEs) at deformation temperatures ranging from T_g to T_g + 25 °C. The strain recovery ratios increased with the increase of deformation speed and with the decrease in maximum strain. The recovery ratios also increased with increasing fixing speed. Therefore, in practical applications, in order to obtain better SMEs, the SMPU should be cooled to its frozen state as soon as possible after being deformed at a high temperature. The ‘fixity’ dramatically increased with the decrease in fixing temperature. To obtain optimal SMEs, the polymer has to be reheated up to the temperature at which the polymer deformed. In addition, the recovery ratios of the SMPU could increase slightly with the increase of recovery time. Copyright © 2004 Society of Chemical Industry     

Polyethylenimine‐Based Shape Memory Polyurethane with Low Transition Temperature and Excellent Memory Performance

Flexible shape memory polyurethanes (SMPUs) are the favorable candidates as a coating or substrate for wearable smart textiles, electronics, and biomedical applications. However, conventional SMPUs (e.g., 1,4 butanediol (BDO)‐based) are not suitable in these applications due to high rigidity, poor mechanical properties, low shape recovery, and high transition temperature. Herein, a polyethylenimine (PEI)‐based SMPU with low transition temperature and tailored properties are reported. The synthesized SMPU are characterized, and their properties are compared with BDO‐SMPUs. The chemical structure of PEI is explored to improve thermal and mechanical properties and to assess their effect on shape memory behavior. The bulky nature of PEI plays a critical role in lowering transition temperature and introduces flexibility in the structure at room temperature. A drop in Young's modulus is found from 13.6 MPa in BDO‐SMPU to 6.2 MPa in PEI‐SMPU. Simultaneously, tensile strength is increased from 3.77 MPa in BDO‐SMPU to 11.85 MPa in PEI‐SMPU. Owing to the improved mechanical properties in PEI‐SMPU, 100% shape recovery is observed, which displays a reproducible trend in ten repetitive cycles due to the presence of reversible physical crosslinks. Therefore, it is envisioned that this can serve as a potential shape memory material in smart wearable technologies.     

Lateral flexible linking of polyurethane copolymer and the effect on shape recovery and tensile mechanical properties

Shape memory polyurethane (SMPU), flexibly crosslinked via a polyethyleneglycol (PEG) spacer attached to its side through an allophanate group, was tested for shape memory and compared with a linear SMPU. The new SMPU was composed of 4,4′‐methylenebis(phenylisocyanate) (MDI), poly(tetramethyleneglycol) (PTMG‐2000), and 1,4‐butanediol (BD), and included polyethyleneglycol (PEG‐200) as a spacer. A second MDI, linked to the carbamate group of the first MDI, served as the connecting point for the PEG‐200. Two types of SMPU, differing according to their soft segment (PTMG‐2000) and linker (PEG‐200) contents, were compared in mechanical and shape memory properties. In the best case, a 780% increase in maximum stress was attained without any sacrifice in strain for the new material compared with the linear polymer. In particular, the stress–strain curve showed that the PEG‐crosslinked SMPU had superior tensile mechanical properties. Its shape recovery was as high as 99%, which is the best value we have measured for an SMPU. After four cyclic tests, shape recovery remained greater than 95%. Shape retention of the best SMPU remained above 93% even after four cyclic tests. Here, results demonstrating the extraordinary shape memory properties of these types of SMPU, together with differential scanning calorimetry (DSC) and infrared spectroscopy data, are analyzed and discussed. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

硅烷偶联纳米SiO2改性形状记忆聚氨酯

本文采用经硅烷偶联剂表面处理的纳米SiO2粒子制备了形状记忆聚氨酯／SiO2纳米复合材料。并用SEM、DSC、TGA对其进行分析,考察其形状记忆行为及力学性能。结果表明,形状记忆聚氨酯中加入纳米SiO2后,其热稳定性能提高了,形状回复起始温度(Ti)提高约10℃,形状回复速率提高约3．8倍,而力学性能有所下降。     

液化MDI基形状记忆聚氨酯扩链剂的选择研究

在选定液化MDI和聚己二酸丁二醇酯(PBAG)软段原料的前提下，采用双酚A(FA)、乙二醇(ED)、1，4-丁二醇(BD)、1，6-己二醇(HD)、一缩乙二醇(DE)扩链剂合成了一系列形状记忆聚氨酯(SMPU)；用FT-IR、DSC对样品的结构进行了分析，并考察了它们的形状记忆性能和力学性能。结果发现，扩链剂对SMPU有一定影响，用FA、ED扩链的SMPU具有较好的微相分离，而DE扩链的具有较好的软段结晶性能；FA、HD的SMPU具有较低的形状回复温度和较快的形状回复速率，HD、DE扩链的则具有较好形状固定性能，FA、DE扩链的SMPU循环使用性能较好；同时FA、HD的SMPU具有较高的弹性模量与力学强度。     

Design and development of graphene oxide/shape memory nanocomposite based on hexamethylene diisocyanate mixing segment

Shape memory polymers are remarkable materials renowned for their distinctive ability to fix and recover their original shape in response to specific stimuli. However, the lower shape fixity (SF) of conventional thermally triggered shape memory polyurethane (SMPU) has limited its broad application potential. This study investigates the transformative influence of graphene oxide (GO) nanofillers when incorporated into a linear diisocyanate-based mixing segment SMPU (SMPU-GO). The lower SF issue of SMPU is ingeniously addressed by leveraging the interactive properties of GO with the 4,4′-methylene bis-phenyl diisocyanate hard segment and the introduction of additional physical cross-links via hexamethylene diisocyanate mixing segment. At 1 wt.% GO incorporation, the modulus increased by 178%, an 8% increase in tensile strength, while the elasticity was maintained. Excellent improvement in SF and shape recovery (SR) was attained at 1 wt.% GO incorporated SMPU, and the SMPU nanocomposite showed the highest SF (65%) and SR (100%) at 70°C temperature and 50% strain.     

The effect of soft segment content and linker length on shape recovery and mechanical properties of laterally linked polyurethane copolymer

Lateral flexible linking of shape memory polyurethane (SMPU) by a polyethyleneglycol (PEG) linker through the allophanate linking method was studied, while adjusting the soft segment content and PEG length. The SMPU was composed of 4,4′‐methylenebis(phenylisocyanate) (MDI), poly(tetramethyleneglycol) (PTMG), 1,4‐butanediol (BD), and PEG‐200 as a linker. A second MDI was used to connect the carbamate group of the SMPU chain and PEG. The impact of soft segment content and PEG length on the mechanical properties and shape recovery of two series of SMPU were compared. In the best case, a 545% increase in maximum stress compared to a linear polymer was attained. The flexibly crosslinked SMPUs behave similarly to natural rubber in their stress–strain curve, but their tensile mechanical properties surpassed those of natural rubber. Shape recovery went up to 96%, which is among the best SMPUs tested so far, and shape recovery remained above 90% after four cyclic tests. The extraordinary shape memory results are analyzed and discussed together with DSC and IR data. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electroactive shape memory performance of polyurethane/graphene nanocomposites

A series of electroactive shape memory polyurethane (SMPU) nanocomposites were synthesized from poly(tetramethylene ether) glycol (PTMG), 4,4-methylenebis(phenyl isocyanate) (MDI) and 1,3-butandiol (1,3-BD) with the addition of various amounts of thermally reduced graphenes (TRG) which were chemically modified with allyl isocyanate (iTRG). The effects of iTRG on electroactive shape recovery behaviors as well as the conventional direct heat actuated SMPU material have been studied in terms of morphological, thermal, mechanical, electrical properties and thermomechanical cyclic behavior. It was found that significant increases in electrical conductivity and temperature were obtained high iTRG contents (>2%) to electrically actuate the nanocomposite, along with large increases in glass transition temperature (T_g) and initial modulus with a dramatic drop in elongation at break.     

Shape memory polyurethane-based electrospun yarns for thermo-responsive actuation

Electrospun nanofibrous yarns of shape memory polyurethane (SMPU)-based nanofibers were successfully prepared. The electrospun yarns were analyzed to assess the dependence of mechanical and shape memory properties on the yarn twist angle. The yarn with a 60° twist angle has high compactness and density, leading to increased tensile strength, elastic modulus, and strain energy. In addition, this yarn shows a significant improvement in the shape memory recovery stress compared with the non-twisted SMPU nanofibers. Moreover, thermal stimuli allowed for the 60° twisted yarn to lift a load that is 103 times heavier than itself. This yarn had a shape recovery stress of 0.61 MPa and generated a 7.95 mJ recovery energy. The results suggest the electrospun yarns could be used as actuators and sensing devices in the medical and biological fields.     

Study on the liquefied‐MDI‐based shape memory polyurethanes

A series of liquefied‐MDI‐based polyurethanes having shape memory behavior, with various soft segments, chain extenders, and micro‐phase separation promoters were synthesized. Their morphology and properties were investigated in terms of thermal properties, dynamic mechanical properties, and shape recovery behavior. The results indicate that the soft segment formed with longer chain segment incline to crystallize during the cooling scans and the resulting SMPU have the higher crystallinity. Meanwhile, the chain extenders, which can enhance the polarity of hard segment, incline to have excellent shape memory properties with bigger storage modulus in rubbery state too. It was also found that the micro‐phase separation promoters have great influence on the shape memory behavior due to the enhancement of micro‐phase separation of SMPU. Furthermore, it was proved again that SMPU with longer soft segment and lower hard segment contents usually showed good shape memory behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Carbon nanotube reinforced shape memory polyurethane foam

Multiwalled carbon nanotube (MWCNT)/polyurethane (PU) foams have been synthesized from polypropylene glycol and 2,4/2,6-toluene diisocyanate following the one-shot foaming method in the presence of water as the chemical blowing agent. The effects of CNT content on the performances of the foams have been analyzed in terms of reactivity, mechanical and dynamic mechanical properties, and shape memory properties of the foams. It was found that the cream time, rise time, tensile, and compressive strengths at room temperature, glassy and rubbery state moduli, glass-transitional temperature (T _g), and shape fixity and shape recovery increased with the addition and increasing amount of MWCNT.     

Improved shape memory effects in multiwalled‐carbon‐nano‐tube reinforced thermosetting polyurethane composites

Shape memory thermosetting polyurethane (SMPU) composites containing different amount of multiwalled carbon nanotube (MWCNT) ranging from 0 to 0.250 phr were prepared. The shape memory behavior, tensile stress, and recovery stress were determined by using conventional thermomechanical cycle; however, the modified thermomechanical cycle designated as progressive stretch–relax–stretch (PSRS) cycle was also employed to create shape memory effects in studied composites. The test was carried out in water bath which was equipped with an electric heater, temperature controller, and tensile stress and strain measuring setup. The recovery and tensile stresses both were showing higher values for PSRS samples as compared with conventional samples. Loading of MWCNT improved the recovery stress of SMPU, thereby confirming reinforcing effect. The maximum recovery stress of 2.17 MPa for 0.188 phr MWCNT loading was observed as compared with 1.09 MPa of unreinforced SMPU specimen. The recovery time was also improved on reinforcement as demonstrated in this article. The morphology of fractured surface and degree of dispersion of MWCNT was studied using Field Emission Scanning Electron Microscope. The impact on glass transition temperature was also observed for MWCNT reinforcement on SMPU, which depends on the degree of dispersion and loading of MWCNT in the specimen. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44389.     

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.     

Effect of pore size distribution on compressive behavior of moderately expanded low‐density polyethylene foams

We investigated the effect of the pore size distribution on the compressive behavior for moderately expanded elastic polymer foams. Unlike well‐expanded foams, moderately expanded foams have heterogeneous cellular structures and their mechanical properties can depend on the heterogeneity of cellular structures. To clarify the effect of the pore size distribution on mechanical properties, we prepared a series of low‐density polyethylene (LDPE) foams with different pore size distributions and relative densities as models of moderately expanded elasitc polymer foams. We performed the microscope observations and the uniaxial compression tests of the moderately expanded LDPE foams. The compressive behavior of a foam was primarily determined by the relative density, but we found that the compressive behavior also depends on the pore size distribution, especially in the collapse region. In the collapse region, the compressive stress–strain curves showed clear dependence on the heterogeneities of cellular structures. The broader cell distribution resulted in the stronger strain dependence of the stress in the collapse region. We show that we can reasonably predict the compressive stress–strain curves from the pore size distributions. POLYM. ENG. SCI., 59:510–518, 2019. © 2018 Society of Plastics Engineers     

形状记忆聚氨酯材料研究进展

综述了形状记忆聚氨酯(SMPU)材料的软硬段的改进、复合改性、交联共混改性等国内外的最新研究进展,重点介绍了改变原料配比、改进合成工艺、复合、交联、共混等获得性能更优的SMPU的方法.并对其在医学、纺织、航空等多方面的应用现状和前景进行了概述.     

Preparation of Shape Memory Polyurethane/Hydroxyapatite Nanocomposite Scaffolds by Electrospinning Method and Investigation of Their Microstructure and Physical-Mechanical Properties

ABSTRACT

A facile method was used for fabricating in-situ-polymerized shape memory polyurethane (PU) hydroxyapatite (HA) nanocomposite scaffolds through electrospinning. The chemical structure and hydrogen bonding index (HBI) content were investigated using Fourier transform infrared spectroscopy. The crystalline morphology was analyzed by X-ray diffraction patterns. Differential scanning calorimetry was conducted to determine the glass transition temperature (T_g ) and degree of crystallinity. The results revealed that HA nanoparticles provide significant reinforcement of PU. Furthermore, incorporation of HA nanoparticles improved the shape memory properties of nanocomposites. The effect of HA nanoparticles on PU/HA electrospun fiber diameter, porosity, mechanical, and shape memory properties were examined.     

Synthesis and thermal shock evaluation of porous SiC ceramic foams for solar thermal applications

Reticulated porous ceramics with structural features spanning across multiple length scales are emerging as the primary media in a variety of demanding mass and heat transfer applications, most notably solar-assisted synthetic fuel processing. In this study, we focus on engineering of the open pore silicon carbide (SiC)-based foams in such catalytic applications. We evaluate the mechanical integrity and thermal stability of these porous structures. X-ray tomography analyses of the 3D structures reveal the presence of dual pore size distribution different by up to an order of magnitude in length scale. We further study the effect of thermal shock—induced via water quenching—on the SiC structures and we conclude that the mechanical properties of the ceramic foams are significantly reduced after thermal stress. Comparison of SEM micrographs—before and after thermal shock—reveals that needle-like features appear inside the foam matrix. These elongated defects may be responsible for structural and mechanical weakening.     

Development of polylactide open‐cell foams with bimodal structure for high‐acoustic absorption

In this study, a highly porous and interconnected foam structure was fabricated using compression molding combined with particulate‐leaching technique. The foamed structures were fabricated with polylactide (PLA) and polyethylene glycol (PEG) with salt as the particulate. The pore size of the foam structure is controlled by the particulates size and higher interconnectivity is achieved by the co‐continuous blending morphology of the PLA matrix with the water‐soluble PEG. PLA is a fully bio‐based thermoplastic polymer and is derived from renewable resources, such as cornstarch or sugarcanes. PEG is also fully biodegradable polymer produced from ethylene. Fabricated foams were characterized for cellular, acoustic, and mechanical properties. The acoustic performance of the foams was studied by measuring the normal incident absorption coefficient in accordance with the ASTM E1050 standard. The results show open porosity as high as 88% was achieved and the effect of water‐soluble polymer on cellular properties and acoustic and mechanical performance of the foams was studied. As a result of the secondary porous structure formed into cell walls by water soluble polymer, the overall absorption of fabricated PLA foams was increased to above 90% while the average absorption of the foams remained unchanged. In addition, the resulting acoustic foams are benign and environmentally friendly. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39518.