形状记忆聚氨酯脲/SiO2纳米复合材料的研究

采用原位分散法合成了形状记忆水性聚氨酯脲(SPU)/SiO2复合水分散液.考察了SiO2含量对SPU水分散液性能及其膜的结构与性能的影响.研究发现,随着SiO2含量的增大,SPU水分散液粒径减小;SPU软段Tg增大,软硬段间的微相分离程度降低;SPU膜的拉伸强度和杨氏模量显著增加,断裂伸长率下降;吸水率小幅增大,与水的接触角变化不大.SiO2质量分数低于5%时,SPU水分散液具有较好的稳定性,SiO2的加入能显著提高SPU膜的形状固定率.     

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。     

纳米SiO2/EP复合材料的制备与性能研究

环氧树脂(EP)固化后交联密度高,呈三维网状结构,存在质脆、耐热性和耐冲击性较差等缺陷,从而限制了其应用范围。通过在环氧树脂中添加纳米Si O2,可以起到增强、增韧和提高热稳定性的作用。本文采用物理共混方法浇铸成型制备纳米Si O2/EP复合材料,并用偶联剂KH-550对纳米Si O2进行表面改性。主要研究纳米Si O2粒子的表面处理、分散方法和粒子添加量对纳米Si O2/EP复合材料力学性能的影响。结果表明:纳米Si O2的加入可以提高Si O2/EP复合材料的力学性能,其中采用偶联剂处理与超声波分散结合时纳米Si O2在环氧树脂基体中的分散效果最佳,当纳米Si O2粒子添加量为3%时,复合材料的的综合性能最佳。     

丙烯酸酯类聚氨酯/SiO2纳米复合材料制备及性能研究

用原位聚合法制备丙烯酸酯类聚氨酯/SiO2纳米复合材料,通过透射电子显微镜研究了纳米SiO2在基体中的分散情况,并对材料的力学性能和光学性能进行了研究。结果表明,纳米SiO2在基体中分散很好;当纳米SiO2的质量分数为1.5%时,复合材料的综合力学性能最佳,其拉伸强度、断裂伸长率和冲击强度分别为34.20MPa、56.15%和81.52kJ/m2,与纯丙烯酸酯类聚氨酯相比分别提高了52.75%、81.19%和149%;且该复合材料的透光率在80%以上。     

CE/纳米SiO2复合材料的改性研究

利用纳米SiO2对氰酸酯树脂(CE)进行改性。结果表明,适量的纳米SiO2可提高CE/纳米SiO2复合材料的冲击强度和弯曲强度;选用不同分子尺寸的偶联剂KH-560和SCA-3对纳米SiO2进行表面处理,扫描电镜(SEM)表明,纳米SiO2经偶联剂处理后CE/纳米SiO2复合材料的静态力学性能、动态力学性能都得到了不同程度的提高,特别是经SCA-3处理后的效果更加明显,偶联剂的加入改善了纳米SiO2在CE中的分散状态,使纳米SiO2与CE之间的界面结合强度进一步提高。     

稻壳SiO_2/聚氨酯纳米复合材料的制备及性能研究

将酸处理后稻壳在600℃焚烧,得到比表面积为212 m2/g,纯度99.3%的稻壳SiO2纳米凝聚体,用偶联剂γ-氨丙基三乙氧基硅烷(KH550)改性后,SiO2纳米凝聚体在溶液中以纳米状态分散,大部分粒子尺寸约30~50 nm。将其与聚氨酯(PU)复合,探讨了不同SiO2含量复合材料的力学性能、热分解性能以及吸水性。研究结果表明:与纯PU相比,稻壳SiO2/PU纳米复合材料的力学性能有不同程度的提高,其耐热性能和耐水性明显增强。     

PP/纳米SiO2复合材料的性能与结构

利用熔融共混的方法制备了PP／纳米SiO2复合材料,研究了纳米SiO2的含量对PP／SiO2复合材料力学性能的影响规律,并通过DSC、SUM等测试方法对复合材料的结构进行分析,合理地解释纳米SiO2对复合材料的影响规律。     

水性聚氨酯-SiO_2纳米复合材料研究进展

介绍了水性聚氨酯纳米氧化硅复合材料的优异性能、纳米氧化硅的制备及分散方法、纳米氧化硅水性聚氨酯复合材料的制备方法及测试手段。     

聚合物/纳米SiO2复合材料的研究进展

介绍纳米SiO2的特性、表面改性及分散技术,以及聚合物/纳米SiO2复合材料的制备方法。对近年来聚合物/纳米SiO2复合材料的研究进展情况进行了综述。指出聚合物/纳米SiO2复合材料具有广阔的应用前景,但尚存在许多需进一步深入研究的问题。     

环氧树脂/SiO2纳米复合材料性能的研究

采用直接共混法制备环氧树脂纳米复合材料,研究纳米SiO2的用量对纳米复合材料力学性能、耐热性以及粘度的影响。结果表明,当纳米SiO2用量为3％时,复合材料的综合性能最佳,其中冲击强度为37．9kJ／m^2,弯曲强度为192．8MPa,弯曲弹性模量为4．5GPa,马丁耐热温度为118℃。     

Modified shape memory epoxy resin composites by blending activity polyurethane

A series of modified shape‐memory epoxy resin composites were prepared by blending activity polyurethane (APU). Fourier transform infrared spectroscopy (FTIR), tensile tests, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and fold‐deploy shape memory tests were used to characterize the structure, mechanical, morphology, thermodynamics, and shape memory performance of these materials. FTIR results suggest that APU has been introduced into the resin matrix resin. Tensile test results show that the addition of appropriate APU can increase the elongation at break significantly, compared with neat epoxy. SEM results indicate that the fracture mechanism has changed from brittle to ductile, suggesting that the brittleness of the material has been overcome. DMA results show that modified materials have lower glass transition temperature (T_g) and lower cross‐linking density for shape memory function. Furthermore, the fold‐deploy shape memory tests prove that the materials possess excellent shape memory properties. They can be deformed into different shapes and recover their original shapes fully within 2 min at T_g, while they are hardly affected by ninefold‐deploy cycles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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。     

原位聚合法浇注型聚氨酯弹性体/纳米二氧化硅复合材料的性能

采用原位聚合法制备了浇注型聚氨酯弹性体(CPUE)/纳米SiO2复合材料,研究了牌号分别为Aerosil R 972 和Aerosil 200的气相法纳米SiO2在基于聚四氢呋喃醚二醇(PTMG)、聚己内酯二醇(PCL)体系CPUE中的分散性、贮存稳定性以及复合材料的热稳定性和物理机械性能.结果表明,Aerosil R 972在PTMG和PCL体系中均有较好的分散性和贮存稳定性;Aerosil 200在PCL体系中具有较好的分散性和贮存稳定性,而在PTMG体系中则相对较差.2种纳米SiO2的添加均能提高复合材料的热稳定性,并能显著增强、增韧和提高复合材料的高温使用性能.     

Polyurethanes having shape memory effects

Segmented polyurethanes (PUs) were prepared from polycaprolactone diols (PCLs), 4,4′-diphenylmethane diisocyanate, and 1,4-butanediol, and tested for shape memory effects. Effects of soft segment molecular weight (M_n = 2000, 4000 and 8000), soft segment content (50–90%), and maximum strain (_m = 100, 200, and 600%) on the cyclic tensile properties as well as the dynamic mechanical, and mechanical properties below (25°C) and above (65°C) the shape recovery temperatures were studied. With increasing soft segment contents: i) glassy state modulus increased and rubbery state modulus decreased; ii) hardness increased at room temperature, and decreased at 65°C; iii) recovery strain decreased with PCL 2000, and increased with PCL 8000 based PUs. On the other hand, the increase in soft segment length resulted in: i) increased rubbery state modulus as well as glass state modulus; ii) increased hardness at room and high temperatures; iii) increased recovery strain at high soft segment content. Tensile yielding became clear with increasing soft segment length and content. Strain upon cooling and unloading (_u) and residual strain (_p) increased, and recovery strain (_r) decreased with cycling. Among these, residual strain was most sensitive to the cycling. Most of the cycling effects were confined during the first one or two cycles. These results were interpreted in terms of soft segment-hard segment phase separation and soft segment crystallization.     

The modification of graphene with alcohols and its use in shape memory polyurethane composites

Graphene prepared by the thermal reduction of graphite oxide was modified by reactions with methanol or 1‐butanol using aqueous HBF₄ solution as a catalyst. Results showed that the reaction created hydroxyl groups on the graphene and at the same time reduced the number of defects. Gravimetry, thermogravimetry, X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy showed that the alcohols had reacted with epoxide groups on graphene. Raman spectroscopy showed that the defects in the graphene were repaired through other accompanying reactions. The reinforcing effect of graphene, observed in the tensile properties and the shape memory behavior of graphene/polyurethane composites, was increased when the graphene was modified with methanol. However, decreases in density and glass transition temperature were evident for the composites made with alcohol‐modified graphene. These results show that the newly created hydroxyl groups on graphene produce effective covalent bonds with the polyurethane chains of the matrix; however, the increased number of bonds restricts the rearrangement of the matrix molecules for dense packing. The covalent bonds between graphene and polyurethane chains enhanced shape recoverability and reduced the hysteresis brought about by repeated thermomechanical cycles. Copyright © 2012 Society of Chemical Industry     

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     

Morphology and properties of shape memory thermoplastic polyurethane composites incorporating graphene‐montmorillonite hybrids

A novel hybrid containing graphene oxide (GO) and montmorillonite (MMT) was first synthesized by solution reaction. Then shape memory thermoplastic polyurethane (TPU) composites incorporating MMT–GO hybrid was fabricated via melt blending. Infrared spectra indicated that GO and MMT have been combined together through chemical hydrogen bonding. Tensile tests showed that MMT‐GO hybrids provided substantially greater mechanical property enhancement than using MMT or GO as filler alone. With only 0.25 wt % loading of MMT–GO hybrid (the mass ratio of MMT:GO is 1:1), there was a relatively high improvement in tensile properties of TPU composites, compared with those of TPU/GO and TPU/MMT composites at the same filler content. Thermal analysis indicated that MMT‐GO hybrids enhanced the thermal decomposition temperatures of TPU composites. Shape memory property tests showed that the shape fixing rate of TPU composites was effectively enhanced by incorporating MMT–GO hybrid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46149.     

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.     

Crosslinked polyurethanes with shape memory properties

A series of shape memory polyurethanes (SMPUs) was prepared from polycaprolactone diol (PCL) 4000, 1,4‐butanediol (BDO), dimethylol propionic acid (DMPA), triethylamine, and 4, 4′‐diphenylmethane diisocyanate (MDI), to which excess MDI or glycerin were added to obtain crosslinked shape memory polyurethanes. Their mechanical, thermomechanical, thermal and shape memory properties were investigated by using differential scanning calorimetry (DSC), Fourier‐transform (FT‐IR) spectroscopy, dynamic mechanical analysis (DMA) and tensile testing. The results showed that crosslinked SMPUs have better thermal and thermomechanical properties than those prepared from linear polyurethanes and display good shape memory effects. Copyright © 2005 Society of Chemical Industry     

High-efficiency shape memory copolymers of polycaprolactone/thermoplastic polyurethane fabricated via in situ ring-opening polymerization

Shape memory blends of polycaprolactone/thermoplastic polyurethane (PCL/TPU) were prepared by in situ ring-opening polymerization (ROP) of ε-caprolactone (CL) and thermoplastic polyurethane (TPU). Fourier infrared spectrometer and ¹H-NMR were used to characterize the chemical structure of PCL/TPU copolymers. The results show that TPU has been involved in the ROP of CL, leading to the formation of copolymers with homogeneous morphologies. Besides, pure PCL and all the blends exhibit an excellent shape fixation ratio of 100%, due to their high crystallinity. When a small amount of TPU is introduced, the crystallinity of PCL decreases, and as a result, the shape recovery ratio of the copolymer is enhanced compared with pure PCL. However, with the increased loading of TPU, the content of PCL as the reversible phase decreases and the storage modulus of the PCL/TPU blend declines, so the driving force for the blends to return from the temporary shape to the initial shape becomes smaller, leading to a decrease in the shape recovery ratio. Notably, when the amount of TPU is only 5%, the shape recovery ratio of the blend could reach 83.3%, which is 26% higher than that of pure PCL, and meanwhile, the tensile strength of the blend decreases slightly. This study provides a new strategy for the design of shape-memory materials with high shape-memory properties.