基于Diels-Alder反应的自修复聚氨酯的结构与修复行为

采用呋喃封端的聚氨酯预聚体与双马来酰亚胺反应,合成了基于Diels-Alder(DA)反应的热可逆自修复聚氨酯(PU-DA).利用FTIR、DSC和gel-solution-gel方法对其分子结构、热性能及其可逆性进行了表征,结果表明,具有热可逆性的DA键被成功引入到聚氨酯中,从而赋予聚氨酯具有良好的再加工性能和自修复性能.通过偏光显微镜观测对材料的自修复行为进行了考察,结果表明,由于DA反应的热可逆性,0.5 mm深度划痕的聚氨酯试样在120℃热处理300 s或130℃热处理150 s后划痕便可消失,从而实现了划痕的自修复.并且模拟实际生活中聚合物材料受到轻微损伤时的情况,通过拉伸试验对0.5 mm深度划痕有效自修复的热处理温度和时间进行了确定,并对同一受损部位多次刻划-修复的修复效率进行了详细研究,结果表明:在120℃处理15 min可达到最佳修复效果,其一次修复效率可达71%,同一受损部位经过3次刻划—修复后,其修复效率仍能达到35%.     

具有自修复和形状记忆功能的聚氨酯光敏树脂

利用封端剂的动态可逆特性,设计、制备出含有多处大位阻脲键和结晶性软段的光敏聚氨酯丙烯酸酯(PUTA).光固化后的材料具有较高的弹性、良好的力学性能、自修复性能和形状记忆性能.经热处理修复后,试样的修复效率达70％(拉伸强度3.58?MPa,伸长率250％);软段的结晶转变使材料具有重复塑形以及形状记忆性能,并可在升温后...     

单壁碳纳米管-氧化石墨烯复合修饰电极测定邻苯二酚

制备了用于测定邻苯二酚的单壁碳纳米管-氧化石墨烯复合修饰玻碳电极.用循环伏安法研究了邻苯二酚在该电极上的电化学行为.结果表明,该修饰电极对邻苯二酚具有良好的电催化性能.在最佳实验条件下,采用差分脉冲伏安法对邻苯二酚进行了测定,其氧化峰电流与邻苯二酚浓度在2×10~(-6)~1×10~(-4) mol/L范围内呈线性关系,相关系数为0.996 2,检出限为4×10~(-7) mol/L.该电极具有良好的重现性,用于模拟废水中邻苯二酚的测定结果令人满意.     

橡胶基多效协同自修复防水复合材料的研究

制备了环氧树脂改性高吸水纤维,随后将改性纤维与天然橡胶通过混、流延、压延、硫化等工艺制备了环境友好型三层复合自修复防水材料,通过SEM、FT-IR、TY-8000万能材料试验机、BTS-001电动不透水仪等考察了自修复防水材料的微观结构、机械性能、抗氧化性能、自修复性能及防渗透性能等。结果表明,高吸水纤维有助于提高其拉伸强度,最大拉伸强度为1.83MPa,断裂伸长率达到700%以上。防水材料完全切断,自修复24h后,其切口部分无可见痕迹,裂口完全愈合,且24h内无水滴渗漏。自修复48h后拉伸强度可达原始材料的2.36倍,断裂伸长率达到80%左右。     

石墨烯包覆碳纳米管-硫(CNT-S)复合材料及锂硫电池性能

针对锂硫电池研究与实际应用中遇到的主要问题, 本文通过一种简单有效的水热法还原氧化石墨烯对商用碳纳米管-硫(CNT-S)纳米复合材料进行包覆, 形成一种可有效抑制多硫聚合物扩散的石墨烯包覆结构。X射线衍射(XRD), 扫描电子显微镜(SEM)表征结果表明硫均匀地负载在碳纳米管上, 并且在CNT-S复合材料外表面包覆有一层石墨烯。电化学测试结果表明, 这种包覆结构能显著提高CNT-S复合材料的锂硫电池性能。     

石墨烯包覆碳纳米管-硫(CNT-S)复合材料及锂硫电池性能

针对锂硫电池研究与实际应用中遇到的主要问题,本文通过一种简单有效的水热法还原氧化石墨烯对商用碳纳米管-硫(CNT-S)纳米复合材料进行包覆,形成一种可有效抑制多硫聚合物扩散的石墨烯包覆结构。X射线衍射(XRD),扫描电子显微镜(SEM)表征结果表明硫均匀地负载在碳纳米管上,并且在CNT-S复合材料外表面包覆有一层石墨烯。电化学测试结果表明,这种包覆结构能显著提高CNT-S复合材料的锂硫电池性能。     

简易方法制备交叉碳纳米管-石墨烯异质结

发展了一种通过两次高分子辅助转移和选择性氧等离子体刻蚀技术大量制备交叉碳纳米管-石墨烯异质结的无损方法. 拉曼光谱和导电性测试证明, 制备的单层石墨烯薄片在大面积范围内质量均一、导电性好. 而且, 本文所讨论的单层石墨烯的生长和随后的器件制备也提供了大面积制备石墨烯薄片图案化的可重复性方法. 该方法与传统的薄膜技术兼容, 只需简易的几步便可把图案化的石墨烯集成到大规模的微电子器件回路中, 有望实现流线型和自动化的石墨烯微电子器件的大量生产. 这些研究结果为进一步制备分子整流器和其它功能纳米/分子器件提供了技术基础.     

拉伸诱导的自修复铂配合物薄膜的发光变化

通过接枝含醛基的铂配合物Pt(N^C^N)Cl(N^C^N=1,3-二吡啶基苯)到聚二甲基硅氧烷(PDMS)骨架上,制备了一种弹性橙红色薄膜(PDMS-PtL1)。PDMS-PtL1薄膜具有很好的拉伸性(高达1500%的应变),并表现出较好的室温自修复性能。此外,PDMSPt L1薄膜表现出有趣的拉伸诱导的发光变化,拉伸后可以检测到单分子态铂配合物的~3π-π*发射。该弹性薄膜有效避免了铂配合物发光淬灭的现象,并且实现了外力诱导的发射态转换。     

氢键型碳纳米管增强自修复复合材料的制备和表征

使用低聚酸、二乙烯三胺以及尿素为原料,碳纳米管为增强剂,制备出兼具良好力学性能和室温(30 ℃)自修复性能的氢键型自修复复合材料,同时对材料通过氢键进行自修复的机制进行了合理推测。 首先,对不同碳纳米管添加量的自修复材料进行应力-应变性能测试。 结果发现,随着碳纳米管的添加,材料的应力、应变均有所提高,添加质量分数9%碳纳米管时,材料的应力达到4.1 MPa、应变达到6%以上。 对添加质量分数9%碳纳米管的自修复材料进行表面形态、自修复性能以及热稳定性能测试。 结果表明,碳纳米管与材料有良好的相容性,材料的表面与切面形态相似;在室温下自修复24 h,自修复效率达到100%;10次断裂-修复循环中自修复效率仍能保持90%以上;材料具有良好的热稳定性,最大失重速率下的温度为474.3 ℃。 为下一代类皮肤传感器以及可穿戴智能设备提供了一种选择,为未来该类型自修复聚合物复合材料在高拉伸强度领域的应用奠定了技术基础。     

A Robust Self-healing Polyurethane Elastomer Enabled by Tuning the Molecular Mobility and Phase Morphology through Disulfide Bonds

Elastomers with outstanding strength, toughness and healing efficiency are highly promising for many emerging fields. However, it is still a challenge to integrate all these beneficial features in one elastomer. Herein, an asymmetric alicyclic structure adjacent to aromatic disulfide was tactfully introduced into the backbone of polyurethane(PU) elastomer. Specifically, such elastomer(PU-HPS) was fabricated by polycondensing polytetramethylene ether glycol(PTMEG), isophorone diisocyanate(IPDI) and p-hydroxydiphenyl disulfide(HPS) via one-pot method. The molecular mobility and phase morphology of PU-HPS can be tuned by adjusting the HPS content. Consequently, the dynamic exchange of hydrogen and disulfide bonds in the hard segment domains can also be tailored. The optimized sample manifests outstanding tensile strength(46.4 MPa), high toughness(109.1 MJ/m3), high self-healing efficiency after fracture(90.3%), complete scratch recovery(100%)and good puncture resistance. Therefore, this work provides a facile strategy for developing robust self-healing polymers.     

Thermal Aging Effect on Mechanical Properties of Polyurethane

This study concerns the effect of thermal aging on mechanical properties of polyurethane. Polyurethane samples were exposed at 85° and 120°C under inert atmosphere. Mechanical tests were carried out on these samples the aging period. Tensile tests were performed to see the effect of aging on elastic modulus (E), stress (σ_r), and strain (?_r) at break. It was shown that there are two distinct periods. Due to aging, E and σ_r increase in the first period, then they decrease in the second period. ?_r decreases first and then increases. Fatigue tests were performed on unaged and aged samples. It was shown that the fatigue behavior of polyurethane (PU) is improved the same way during the first stage of aging. In the second step, the number of cycles to failure increases due to aging. The results show that aging has an important effect on mechanical properties of PU. The strain at break decreases during the first step of aging due to post-cross-linking and then increases due to chain scission in the network. Based on these results, the effect of cross-linking and chain scission on the mechanical properties of PU was discussed.     

Modulation of Self-healing of Polyion Complex Hydrogel by Ion-specific Effects

We have prepared polyion complex (PIC) hydrogel consisting of poly(3-(methacryloylami no) propyl-trimethylamonium chloride) and poly(sodium p-styrenesulfonate) polyelectrolytes via a two-step polymerization procedure and have investigated specific ion effects on the selfhealing of the PIC hydrogel. Our study demonstrates that the mechanical properties of the PIC hydrogel are strongly dependent on the type of the ions doped in the hydrogel. The ion-specific effects can be used to modulate the self-healing efficiency of the PIC hydrogel. As the doped anions change from kosmotrops to chaotropes, the self-healing efficiency of the PIC hydrogel increases. A more chaotropic anion has a stronger ability to break the ionic bonds formed within the hydrogel, leading to a higher efficiency during the healing.     

改性纳米炭黑/聚氨酯复合物的制备及表征

利用有机硅偶联剂改性的纳米炭黑和聚氨酯制备了纳米炭黑/聚氨酯复合物. 采用红外光谱、透射电镜、流变学及力学性能等测试方法对纳米粒子及其聚氨酯复合物进行了表征. 红外光谱表明, 纳米粒子的存在使聚氨酯的氢键结构发生了改变. 适量改性纳米炭黑粒子明显提高了聚氨酯的拉伸强度和断裂伸长率等力学性能. 流变学测试结果表明, 溶液中改性纳米炭黑粒子与聚氨酯分子间存在明显的相互作用.     

静电纺丝制备自修复功能纤维及其自愈合性能表征

应用静电纺丝技术,以聚苯乙烯和愈合剂的共混溶液为纺丝液,制备了含有愈合剂的功能纤维,并以其制备了具有自修复性能的纤维/树脂复合材料.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、荧光显微镜等对纤维的形貌和结构进行了表征,探讨了纺丝溶液的组成对纤维形貌和结构的影响.纤维中愈合剂的含量随纺丝液中愈合剂浓度的增加而增大,但可纺性随之变差.通过SEM观察了所制备的复合材料表面预制裂纹的修复,在一定温度下裂纹处纤维中的愈合剂(分别为环氧和其固化剂)释放并进一步反应,经过愈合复合材料的拉伸强度提高了2.81 MPa,力学性能明显改善.     

环氧丁羟型聚氨酯弹性体的制备与性能

以间氯过氧苯甲酸(mCPBA)为氧化剂对降解法制备的端羟基聚丁二烯(DHTPB)中的部分双键进行环氧化改性,通过控制mCPBA和双键的比例制得具有不同环氧率的环氧化端羟基聚丁二烯(EHTPB),经1H-NMR分析测试表明EHTPB的环氧率分别为5%、10%和15%,与设计值基本一致.进一步以EHTPB为多元醇、4,4'-二苯基甲烷二异氰酸酯(MDI)为异氰酸酯、1,4-丁二醇为扩链剂制备了环氧丁羟型聚氨酯弹性体(EPU),并对其性能进行了测试,研究结果表明:丁羟胶的环氧化改性对聚氨酯弹性体的力学性有着一定的提升作用,其杨氏模量和拉伸强度随环氧率的上升而提高,而断裂伸长率则随环氧率的上升有所下降;环氧丁羟型聚氨酯弹性具有优异的弹性恢复能力;环氧化改性后,聚氨酯弹性体的热稳定性有一定程度的提高;聚氨酯弹性体的玻璃化转变温度随环氧率的上升而升高.     

Processing and Characterization of Polypropylene Filled with Multiwalled Carbon Nanotube and Clay Hybrid Nanocomposites

Nanocomposites reinforced with hybrid fillers of carbon nanotubes (CNTs) and clays were developed, aiming at enhancing the dispersion of nanofillers with balanced mechanical properties while lowering the cost of the final product. Polypropylene-based nanocomposites were prepared by the master batch dilution technique with varying combinations of CNTs and clays as fillers by using commercially available highly concentrated master batches of polypropylene/organoclays and polypropylene/multiwalled carbon nanotubes using high-shear twin-screw extrusion. Their mechanical and morphological properties were then evaluated. It was shown that the addition of hybrid filler to polypropylene enhanced the ductility and flexural properties of nanocomposites, confirming the synergistic effect of nanofillers as a multifunctional fillers. The novelty of this work lies in the synergy arising from the combination of two nanofillers with unique dimensions and aspect ratios as well as different dispersion characteristics, which have not been specifically considered previously.     

Preparation and characterization of functionalized graphene oxide/carbon fiber/epoxy nanocomposites

Graphene oxide (GO) was functionalized using three different diamines, namely ethylenediamine (EDA), 4,4′-diaminodiphenyl sulfone (DDS) and p-phenylenediamine (PPD) to reinforce an epoxy adhesive, with the aim of improving the bonding strength of carbon fiber/epoxy composite. The chemical structure of the functionalized GO (FGO) nanosheets was characterized by elemental analysis, FT-IR and XRD. Hand lay-up, as a simple method, was applied for 3-ply composite fabrication. In the sample preparation, the fiber-to-resin ratio of 40:60 (w:w) and fiber orientations of 0°, 90°, and 0° were used. The GO and FGO nanoparticles were first dispersed in the epoxy resin, and then the GO and FGO reinforced epoxy (GO- or FGO-epoxy) were directly introduced into the carbon fiber layers to improve the mechanical properties. The GO and FGO contents varied in the range of 0.1–0.5 wt%. Results showed that the mechanical properties, in terms of tensile and flexural properties, were mainly dependent on the type of GO functionalization followed by the percentage of modified GO. As a result, both the tensile and flexural strengths are effectively enhanced by the FGOs addition. The tensile and flexural moduli are also increased by the FGO filling in the epoxy resin due to the excellent elastic modulus of FGO. The optimal FGO content for effectively improving the overall composite mechanical performance was found to be 0.3 wt%. Scanning electron microscopy (SEM) revealed that the failure mechanism of carbon fibers pulled out from the epoxy matrix contributed to the enhancement of the mechanical performance of the epoxy. These results show that diamine FGOs can strengthen the interfacial bonding between the carbon fibers and the epoxy adhesive.     

Dielectric,mechanical and electro-stimulus response properties studies of polyurethane dielectric elastomer modified by carbon nanotube-graphene nanosheet hybrid fillers

The typical nano-carbon materials, 1D fiber-like carbon nanotubes (CNTs) and 2D platelet-like graphene nanosheets (GRNs), that have attracted tremendous attention in the field of polymer nanocomposites due to their unprecedented properties, are used as conducting filler to induce a considerable improvement in the mechanical, thermal and electrical properties of the resulting graphene/polymer nanocomposites at very low loading contents. This study deals with the preparation and electro-stimulus response properties of polyurethane (PU) dielectric elastomer films with such 1D and 2D nanocarbon fillers embedded in the polymer matrix. The various forms of carbon used in composite preparation include CNT, GRN and CNT-GRN hybrid fillers. Results indicate that the dielectric, mechanical and electromechanical properties depend on the carbon filler type and the carbon filler weight fraction. Here, it has been also established that embedding CNT-GRN hybrid fillers into pristine polyurethane endows somewhat better dispersion of CNTs and GRNs as well as better interfacial adhesion between the carbon fillers and matrix, which results in an improvement in electric-induced strain. Therefore, the nanocomposites seem to be very attractive for microelectromechanical systems applications.