磁、热双重响应的Fe3O4/EUG形状记忆复合材料的制备

将Fe3O4纳米粒子通过机械加工使其分散在杜仲胶（EUG）基体中，制备磁、热双响应形状记忆Fe3O4/EUG复合材料。探究Fe3O4纳米粒子含量与EUG硫化胶的升温速率、磁响应形状回复、Fe3O4纳米粒子的分散状态及力学性能之间的关系。结果表明，在添加Fe3O4纳米粒子超过30 phr后，Fe3O4在硫化EUG基体中有轻微团聚现象。Fe3O4具有补强作用，Fe3O4/EUG复合材料在高温（Tm+20 ℃）下力学性能均有提高，Fe3O4/EUG-50比EUG的拉伸强度提升了47%。经DMA测试，Fe3O4/EUG复合材料在三次循环下的固定率和回复率均在98%以上。Fe3O4/EUG复合材料在感应磁场中随着Fe3O4添加量增加样条温升速度提高，可实现快速无接触式加热，最短在12 s即可实现形状回复。     

Thermal and mechanical properties of poly(ε‐caprolactone)/polyhedral oligomeric silsesquioxane nanocomposites

Poly(ε‐caprolactone) (PCL)/trisilanolphenyl polyhedral oligomeric silsesquioxane (TspPOSS) nanocomposites were prepared by solution mixing followed by film casting. Wide‐angle X‐ray diffraction and field‐emission scanning electron microscopy observations showed that the POSS molecules formed crystal domains and dispersed uniformly on the nanoscale in the PCL matrix. Fourier transform infrared analysis of the nanocomposites revealed that there are hydrogen‐bonded interactions between the silanol group of the TspPOSS and carbonyl oxygen of the PCL. Differential scanning calorimetry, tensile testing, and dynamic mechanical analysis (DMA) showed that, with increasing POSS content in the nanocomposites, the melting temperature and degree of crystallinity decreased while glass transition temperature, tensile modulus and strength increased without sacrificing the ductility of the PCL. DMA results also demonstrated the presence of a rubbery plateau above the melting temperature of the PCL/TspPOSS nanocomposites, and the moduli at the plateau region increased with increasing POSS content in the nanocomposites, implying that the PCL/TspPOSS nanocomposites formed a physically crosslinked structure. The physically crosslinked PCL/TspPOSS nanocomposites exhibited a thermally triggered shape memory effect. Copyright © 2012 Society of Chemical Industry     

Biodegradable magnetic‐sensitive shape memory poly(ɛ‐caprolactone)/Fe3O4 nanocomposites

A novel biodegradable magnetic‐sensitive shape memory poly(?‐caprolactone) nanocomposites, which were crosslinked with functionalized Fe₃O₄ magnetic nanoparticles (MNPs), were synthesized via in situ polymerization method. Fe₃O₄ MNPs pretreated with γ‐(methacryloyloxy) propyl trimethoxy silane (KH570) were used as crosslinking agents. Because of the crosslinking of functionalized Fe₃O₄ MNPs with poly(?‐caprolactone) prepolymer, the properties of the nanocomposites with different content of functionalized Fe₃O₄ MNPs, especially the mechanical properties, were significantly improved. The nanocomposites also showed excellent shape memory properties in both 60 °C hot water and alternating magnetic field (f = 60, 90 kHz, H = 38.7, 59.8 kA m^?1). In hot water bath, all the samples had shape recovery rate (R_r) higher than 98% and shape fixed rate (R_f) nearly 100%. In alternating magnetic field, the R_r of composites was over 85% with the highest at 95.3%. In addition, the nanocomposites also have good biodegradability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45652.     

Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Synthesis and properties of novel biodegradable poly(ε‐caprolactone)/ poly(ethylene glycol)‐based polyurethane elastomers

Elastomeric polyurethanes with tunable biodegradation properties and suitable for numerous biomedical applications were synthesized via reaction of epoxy‐terminated polyurethanes (EUPs) with 1,6‐hexamethylenediamine as curing agent. The EUPs themselves were prepared from glycidol and isocyanate‐terminated polyurethanes made from poly(ε‐caprolactone) (PCL) or poly(ethylene glycol) (PEG) and 1,6‐hexamethylene diisocyanate. All the polymers were characterized by conventional methods, and their physical, mechanical, thermal, and degradation properties were studied. The results showed that the degradation rate and mechanical properties of the final products can be controlled by the amount of PEG or PCL present in the EUP. Increasing the PEG content causes an increase of hydrolytic degradation rate, and increasing the PCL content improves the mechanical properties of the final products. Evaluation of cytotoxcicity showed nontoxic behavior of the prepared samples, but the cytocompatibility of these polymers needs to be improved. Copyright © 2006 Society of Chemical Industry     

Fe3O4/聚甲基丙烯酸羟乙酯改性磁性微球对Al3+的吸附

以乙二醇二甲基丙烯酸酯为交联剂,采用悬浮聚合法制备Fe3O4/聚甲基丙烯酸羟乙酯磁性微球(mPHEMA),并经改性后制得一种新型吸附剂(M-mPHEMA).采用扫描电镜、X射线衍射、元素分析等对其进行了表征,并考察了它对Al3+的吸附性能.结果表明,制备的球形磁性吸附剂粒径45～70μm,对Al3+的饱和吸附容量为428μmol/g.pH 5～7时吸附容量最大.对饮用水的测试结果表明,M-mPHEMA对Al3+的去除率达98%,高于其他离子.用1 mol/L HNO3脱附,Al3+脱附率达98.5%,吸附剂有良好的重复使用性.     

Synthesis and characterization of novel conducting composites of Fe3O4 nanoparticles and sulfonated polyanilines

Surface charged iron oxide (Fe₃O₄) nanoparticles were used for the synthesis of sulfonated polyaniline (SPAN)‐Fe₃O₄ nanocomposites (SPAN/Fe₃O₄‐NCs). 2,5‐diaminobenzenesulfonic acid (DABSA) and 2‐aminobenzenesulfonic acid (ABSA) were independently polymerized with aniline to form SPAN. The structure of the composites was characterized by means of transmission electron microscopy (TEM), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectra, conductivity and magnetic properties. TEM reveals that Fe₃O₄ nanoparticles are “glued” with SPAN in the composite. TGA indicates that SPAN/Fe₃O₄‐NCs are having better thermal stability. The room temperature conductivity of SPAN/Fe₃O₄‐NCs is higher than that of pristine PANI and SPAN. SPAN/Fe₃O₄‐NCs exhibits magnetic behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4127–4134, 2007     

Characterization of nanocellulose‐ reinforced shape memory polyurethanes

BACKGROUND: Shape memory polymers are capable of fixing a transient shape and of recovering their original dimensions by the application of an external stimulus. Their major drawback is their low stiffness compared to smart materials based on metals and ceramics. To overcome this disadvantage, nanocellulose was utilized as reinforcement. RESULTS: Composites were prepared by casting stable nanocellulose/segmented polyurethane suspensions. The heat of melting of the polyurethane soft segment phase increased on cellulose addition. Composites showed higher tensile modulus and strength than unfilled films (53% modulus increase at 1 wt% nanocellulose), with higher elongation at break. Creep deformation decreased as cellulose concentration increased (36% decrease in 60‐minute creep by addition of 1 wt% nanocellulose). The nanocomposites displayed shape memory properties equivalent to those of the neat polyurethane, with recoveries of the order of 95% (referred to second and further cycles). CONCLUSIONS: It is possible to markedly improve the rigidity of shape memory polymers by adding small amounts of well‐dispersed nanocellulose. However, this improvement did not have substantial effects on the material shape fixity or recovery. Shape memory behavior seems to continue to be controlled by the polymer properties. Copyright © 2007 Society of Chemical Industry     

冻融法制备微米级Fe3O4/聚乙烯醇磁性水凝胶及其磁力学性能研究

以微米级Fe3O4粉末和聚乙烯醇(PVA)为原料,采用反复冷冻-融化技术(冻融)制备了Fe3O4/PVA磁性水凝胶,研究了磁性水凝胶的力学性能、磁场阈值,磁性能等随Fe3O4的含量及冻融次数的变化行为,并使用扫描电子显微镜(SEM)以及X射线衍射(XRD)分别研究了Fe3O4/PVA磁性水凝胶的微观形貌和结晶性能.结果表明随冻融循环次数的增加,Fe3O4/PVA磁性水凝胶的力学性能、磁场阈值,及磁性能等均随Fe3O4的含量及冻融次数显著变化;Fe3O4在磁性水凝胶中分布均匀,PVA水凝胶经反复冷冻-融化后结晶性能有所提高.     

Shape‐memory effects of radiation crosslinked poly(ϵ‐caprolactone)

Poly(?‐caprolactone) (PCL) with different molecular weight were crosslinked by γ‐radiation. The radiation crosslinking features were analyzed by Soxhlet extraction with toluene and the Charlesby–Pinner equation. The crosslinking degree is relative to molecular weight and radiation dose; the relation between sol fraction and dose follows the Charlesby–Pinner equation. All the samples were crystalline at room temperature, and the radiation crosslinking had a little effect on the crystallinity and the melting behavior of PCL. The shape‐memory results indicated that only those specimens that had a sufficiently high crosslinking degree (gel content is higher than about 10%) were able to show the typical shape‐memory effect, a large recoverable strain, and a high final recovery rate. The response temperature of the recovery effect (about 55°C) was related to the melting point of the samples. The PCL shape‐memory polymer was characterized by its low recovery temperature and large recovery deformation that resulted from the aliphatic polyester chain of PCL. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1589–1595, 2003     

Synthesis and properties of shape memory graphene oxide/polyurethane chemical hybrids

Graphene oxide modified chemically with allyl isocyanate (iGO) was incorporated in various amounts into acrylate‐terminated polyurethane (PU) via UV curing. The effects of this incorporation on the morphological, mechanical, dynamic mechanical, thermal and shape memory properties of the resulting hybrids were examined. The iGO nanoparticles incorporated into the PU chains acted as both multifunctional crosslinks and reinforcing fillers, and the effects were most pronounced at low iGO contents (0.5 and 1.0 wt%). Consequently, the glassy and rubbery state moduli, yield strength, glass transition temperature, shape fixity and shape recovery ratios were increased on adding up to 1 wt% iGO. At higher iGO loadings, the values of most of these properties decreased due to aggregation and the auto‐inhibition of allyl compounds. © 2013 Society of Chemical Industry     

Au/Fe3O4纳米复合材料的制备及其催化性能

通过将金纳米粒子铆接到Fe3O4载体表面,制得了Au/Fe3O4纳米复合粒子。首先以对苯二酚为还原剂还原HAuCl4制得球形金纳米粒子;然后采用溶剂热法制备Fe3O4磁性纳米颗粒,并用巯基丙酸(MPA)对其修饰;最后通过MPA与金纳米粒子之间的相互作用,将金纳米颗粒固定到Fe3O4表面。采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)和振动样品磁强计(VSM)和紫外-可见分光光度计(UV-vis)对所制备材料进行形貌、晶型、磁性和催化性能的表征。结果表明,金纳米颗粒成功包覆在Fe3O4表面,所得到的Au/Fe3O4复合纳米材料具有单分散性和超顺磁性,并且对NaBH4还原对硝基苯酚(4-NP)制备对氨基苯酚(4-AP)的反应显示出优良的催化性能。     

Effective preparation and characterization of montmorillonite/poly(ε‐caprolactone)‐based polyurethane nanocomposites

In this study, montmorillonite (MMT)/poly(?‐caprolactone)‐based polyurethane cationomer (MMT/PCL‐PUC) nanocomposites were prepared and their mechanical properties, thermal stability, and biodegradability were investigated. PCL‐PUC has 3 mol % of quaternary ammonium groups in the main chain. The MMT was successfully exfoliated and well dispersed in the PCL‐PUC matrix for up to 7 wt % of MMT. The 3 mol % of quaternary ammonium groups facilitated exfoliation of MMT. The 1 wt % MMT/PCL‐PUC nanocomposites showed enhanced tensile properties relative to the pure PCL‐PU. As the MMT content increased in the MMT/PCL‐PUC nanocomposites, the degree of microphase separation of PCL‐PUC decreased because of the strong interactions between the PCL‐PUC chains and the exfoliated MMT layers. This resulted in an increase in the Young's modulus and a decrease in the elongation at break and maximum stress of the MMT/PCL‐PUC nanocomposites. Biodegradability of the MMT/PCL‐PUC nanocomposites was dramatically increased with increasing content of MMT, likely because of the less phase‐separated morphology of MMT/PCL‐PUC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization behavior of poly(ε‐caprolactone)/layered double hydroxide nanocomposites

Poly(?‐caprolactone) (PCL)/layered double hydroxide (LDH) nanocomposites were prepared successfully via simple solution intercalation. The nonisothermal melt crystallization kinetics of neat PCL and its LDH nanocomposites was investigated with the Ozawa, Avrami, and combined Avrami–Ozawa methods. The Ozawa method failed to describe the crystallization kinetics of the studied systems. The Avrami method was found to be useful for describing the nonisothermal crystallization behavior, but the parameters in this method do not have explicit meaning for nonisothermal crystallization. The combined Avrami–Ozawa method explained the nonisothermal crystallization behavior of PCL and its LDH nanocomposites effectively. The kinetic results and polarized optical microscopy observations indicated that the addition of LDH could affect the mechanism of nucleation and growth of the PCL matrix. The Takhor model was used to analyze the activation energies of nonisothermal crystallization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Interfacial and mechanical properties of γ‐Fe2O3/segmented polyurethane/poly(vinyl chloride) composites

Segmented polyurethane (SPU)/poly(vinyl chloride) (PVC) blends were particulated with γ‐Fe₂O₃. Interfacial properties of the composite were studied through the adsorption behaviors of SPU and PVC and their blends on γ‐Fe₂O₃ particles surface. Mechanical properties of the composite were measured with dynamic mechanical analysis and tensile test measurements. PVC with functional groups (FPVC), because of strong interactions, showed preferential adsorption on γ‐Fe₂O₃ compared with SPU and PVC. Moreover, the γ‐Fe₂O₃ particles were covered by FPVC in the γ‐Fe₂O₃/SPU/FPVC composite. The adsorption layer of FPVC protected SPU from catalytic degradation by γ‐Fe₂O₃, resulting in increasing hydrolytic stability for SPU. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3030–3035, 2001     

单分散Fe3O4亚微米球的粒径控制合成及表征

采用溶剂热还原法,以FeCl3.6H2O和乙二醇为原料,在200℃相对低温条件下成功合成四氧化三铁微米球。通过改变实验条件,可在115～435nm有效调控Fe3O4亚微米球的粒径。采用X射线衍射仪(XRD)、透射电子显微镜(TEM)和扫描电子显微镜(SEM)对样品的结构、粒径、形貌和组成进行了分析,并于室温测试了它的磁学性能。结果表明,产物Fe3O4亚微米球为反尖晶石结构,330nmFe3O4亚微米球的矫顽力(Hc)为6644.93A/m,饱和磁化强度(Ms)为81.2emu/g,剩余磁化强度(Mr)为14.6emu/g。研究了乙二醇和NaOH的浓度、反应时间对产物形貌的影响,结果表明,乙二醇在Fe3O4亚微米球的形成过程中起着关键作用,并提出了可能的生长机理。     

Biodegradable and photocurable multiblock copolymers with shape‐memory properties from poly(ε‐caprolactone) diol,poly(ethylene glycol), and 5‐cinnamoyloxyisophthalic acid

Biodegradable and photocurable multiblock copolymers of various compositions were synthesized by the high‐temperature solution polycondensation of poly(ε‐caprolactone) (PCL) diols of molecular weight (M_n) = 3000 and poly(ethylene glycol)s (PEG) of M_n = 3000 with a dichloride of 5‐cinnamoyloxyisophthalic acid (ICA) as a chain extender, followed by irradiation by a 400 W high‐pressure mercury lamp (λ > 280 nm) to form a network structure. The gel contents increased with photocuring time, reaching a level of over 90% after 10 min for all copolymers without a photoinitiator. The thermal and mechanical properties of the photocured copolymers were examined by DSC and tensile tests. In cyclic thermomechanical tensile tests, the photocured ICA/PCL/PEG copolymer films showed good shape‐memory properties at 37–60°C, with both shape fixity ratio and shape recovery ratio over 90% at a maximum tensile strain of 100–300%. The water absorption of these copolymers and their rate of degradation in a phosphate buffer solution (pH 7.0) at 37°C increased significantly with increasing PEG content. The novel photocured ICA/PCL/PEG multiblock copolymers are potentially useful in biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology and electrical properties of carbon‐black‐filled poly(ϵ‐caprolactone)/poly(vinyl butyral) nanocomposites

The morphology of poly(ε‐caprolactone) (PCL)/poly(vinyl butyral) (PVB)/clay nanocomposites was studied as a function of a small amount of amorphous PVB by polarized optical microscopy. The band spacings of PCL spherulites in PCL/PVB/clay nanocomposites decreased with increasing PVB content, and this indicated that increasing the PVB content shortened the period of lamellar twisting. The electrical properties of PCL/PVB/clay nanocomposites containing carbon black (CB) were also measured as a function of the PVB content. For samples with the same CB content, the intensity of the positive temperature coefficient (defined as the ratio of the peak resistivity to the resistivity at room temperature) of the nanocomposites increased as the PVB content increased. The change in the positive temperature coefficient was related to the morphological differences (i.e., the period of lamellar twisting) in the nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1022–1031, 2003