基于配位键交联的自修复弹性体的合成及表征

通过八甲基环四硅氧烷(D_4)的开环平衡反应合成了端氨基聚二甲基硅氧烷(APTPDMS),随后将APT-PDMS与二异氰酸酯反应生成预聚体,以2,6-二氨基吡啶(2,6-DAP)为扩链剂,合成得到有机硅弹性体(PDMS-PU),最后以Fe~(3+)进行配位交联,制备了一系列自修复有机硅弹性体(PDMS-PU/M)。通过核磁共振、红外和紫外-可见光谱、万能试验机、激光共聚焦显微镜分析表征了产物结构和材料的力学性能、自修复性能。结果表明:PDMS-PU/M具有优异的力学和自修复性能,拉伸强度可达1.96 MPa,自修复效率可达82.7%;通过控制Fe~(3+)的含量,改变交联密度,可以实现材料强度和柔性之间的调节。     

基于聚合物复合物的自修复与可修复聚合物材料

聚合物材料在使用过程中受到损伤,就会丧失原有的力学强度和功能.修复功能能够延长聚合物材料的使用寿命、减少原料浪费并提高材料性能的可靠性.赋予聚合物材料修复性能是可持续发展社会对聚合物材料设计的重要需求.本文系统地介绍了本研究组发展的基于溶液中复合的聚合物复合物构筑自/可修复聚合物材料的方法,以及基于高密度的超分子可逆作用力及聚合物复合原位生成的纳米粒子的协同,解决聚合物复合材料的良好修复性能与高力学强度之间矛盾的策略.基于聚合物复合的方法,我们成功制备了聚合物凝胶、弹性体及高强度聚合物复合材料,并实现了上述修复材料在防雾、质子传导和传感等方面的功能.聚合物复合的方法为制备具有优异力学性能和功能的自/可修复聚合物材料提供了新思路.     

氮化硼/聚合物导热复合材料研究进展

电子信息产业的高速发展,使得电子装置或装备在使用过程中产生的热量越来越剧烈,需要及时导出以保证其正常运行,聚合物基导热复合材料由于其优异的加工性和较低的成本得到了应用。六方氮化硼(hBN)兼具优异的导热性和绝缘性,因此作为导热填料在导热绝缘聚合物复合材料领域受到越来越多的关注。本文主要从氮化硼填料尺寸、表面性质、取向结构以及杂化等方面综述了近年来氮化硼/聚合物导热复合材料的研究进展。     

磺化石墨烯/天然橡胶复合材料的性能研究

以磺化石墨烯为填料,将其填充到天然胶乳中,混合均匀后共沉淀,采用传统橡胶加工方法制备了天然橡胶复合材料。对磺化石墨烯的结构和形貌进行了表征,测定了硫化胶的力学性能、耐磨性能、透气性能和导热性能。研究结果表明:磺化石墨烯表面含有丰富的活性官能团,为少层片状结构,硫化胶的力学性能、耐磨性得到了提高,而透气性和导热性有所下降。当石墨烯添加量为2.0%(wt)时,复合材料的拉伸强度最大为27.06MPa;磨耗体积仅为0.08cm~3;导热系数最小为0.42W/(m·K);透气量最低,为1.98×10~(-4)cm~3/(m~2·d·Pa)。     

微胶囊填充型自修复聚合物及其复合材料

微胶囊填充型自修复聚合物及其复合材料是近年来高分子科学界的研究热点之一。本文介绍了含有微胶囊聚合物复合材料自修复的概念和机理,综述了近5年来针对不同基体材料的微胶囊自修复研究情况,包括环氧树脂、乙烯基酯树脂、纤维增强环氧树脂复合材料、弹性体以及聚甲基丙烯酸甲酯等基体材料。本文同时介绍了微胶囊的芯材和壁材、微胶囊的粒径、修复时间和压强等因素对复合材料自修复性能的影响,以及自修复效果的评价方法。最后对微胶囊填充型自修复聚合物及其复合材料的研究前景进行了展望。     

基于可逆酰腙键的自修复聚氨酯的制备与性能研究

由双丙酮醇和对苯二甲酸二酰肼反应生成酰腙键得到羟基封端的功能性扩链剂(命名为AAD)。将亲水性良好且广泛应用于生物医用聚氨酯材料的二官能度多元醇(聚己内酯二元醇PCL-210)和三官能度聚醚多元醇(TEP-240)分别与MDI-50反应生成端异氰酸酯基团的聚氨酯预聚体,将二者按照一定比例混合,并加入AAD交联得到自修复聚氨酯。根据修复前后拉伸强度和断裂伸长率的恢复值表征其自修复性能,表明室温下修复24h后其拉伸强度恢复至94.6%,断裂伸长率恢复至原始试样的76.3%。     

新型乙炔封端聚酰亚胺的制备及性能

用双酚A型二醚二酐(BPADA)和3-乙炔基苯胺(m-APA)进行缩聚反应合成了乙炔基封端的聚酰亚胺预聚体, 并对预聚体的熔体黏度、稳定性和热性能等进行研究. 结果表明, 此类预聚体具有较宽的加工窗口和较低的加工温度, 适合模压成型工艺制备树脂基复合材料. 预聚体经250 ℃固化后显示了优异的热性能, 动态力学分析显示其玻璃化转变温度为363 ℃, 在氮气和空气气氛下5%热失重温度分别为490和492 ℃.     

c-BN对绝缘高导热硅橡胶性能的影响

采用聚二甲基硅氧烷基础胶、含氢硅油交联剂、立方氮化硼(c-BN)导热填料,制备了绝缘高导热硅橡胶;研究了c-BN的不同含量对硅橡胶导热性能、绝缘性能、物理性能的影响。结果表明:填充改性c-BN粉体可以大幅度提高硅橡胶体系的导热性能,在c-BN用量为80%时导热系数为7.16 W/(m·k),热阻为3.39 cm~2K/W;c-BN粉体会降低硅橡胶体系的绝缘性能和力学弹性,但当用量不超过80%时,击穿强度大于6 k V/mm、体积电阻率大于1×1012Ω·cm、硬度小于55、压缩永久变形小于30%,符合实际使用中的绝缘需要,符合产品安装和使用的条件,不易被压碎、压裂而且具有一定弹性。     

改性氧化铝对HDPE/PA6复合材料导热性能的影响

使用硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH550)对氧化铝(Al2O3)进行表面改性,通过傅里叶变换红外光谱仪(FT-IR)、热重分析仪(TG)对改性Al2O3(m-Al2O3)进行了表征。将Al2O3和m-Al2O3分别填充到高密度聚乙烯/尼龙6(HDPE/PA6)共混物中制备复合材料,以提高材料的导热性。利用导热系数仪、维卡软化点测试仪、万能试验机、扫描电子显微镜对复合材料的导热性能、耐热性能、拉伸性能和微观形貌进行了分析和研究。结果表明,复合材料的导热性随着Al2O3含量的增加而逐渐提高,与基体相比,材料的耐热性能、杨氏模量也得到了提高。经过硅烷偶联剂处理后,m-Al2O3能进一步提高复合材料的导热性能、耐热性能和杨氏模量。     

改性低分子量聚异戊二烯橡胶的合成与应用

采用阴离子溶液聚合法合成了低分子量3,4-聚异戊二烯(LPI), 并对其进行改性, 制备了硅氧烷改性的低分子量3,4-聚异戊二烯(MLPI), 将其应用于白炭黑补强的溶聚丁苯橡胶(SSBR)复合材料, 探究了端基改性物LPI-丙基甲基二甲氧基硅烷(LPI-CMDS)、 LPI-丙基三甲氧基硅烷(LPI-CTMS)、 LPI-丙基三乙氧基硅烷(LPI-CTES)和接枝改性物3-巯丙基三乙氧基硅烷接枝改性LPI(LPI-g-MTS)对SSBR复合材料中白炭黑的分散以及硫化胶性能的影响. 混炼胶的应变扫描和结合胶含量分析结果表明, MLPI增强了填料与聚合物之间的相互作用, 改善了白炭黑在复合材料中的分散, 其中LPI-g-MTS因活性位点多, 效果最佳; 与填充LPI的复合材料相比, 硫化胶的物理机械性能, 尤其是填充LPI-g-MTS后硫化胶的300%定伸应力和拉伸强度分别提升了89.66%和27.15%, 这为改善白炭黑在非极性橡胶中的分散提供了一条新途径.     

A Fast and Room-temperature Self-healing Thermal Conductive Polymer Composite

Thermal conducting materials may be damaged during long-term use, resulting in the increase of thermal resistance and therefore inefficient heat dissipation. The introduction of self-healing ability may solve this problem, but the realization of fast and room-temperature selfhealing in thermal conducting composites is quite challenging. Herein, we choose a flexible poly(dimethylsiloxane) polymer material(PDMSCOOH) as the matrix and graphene nanosheets as the thermal conductive filler to prepare a new kind of thermal conductive polymer composite(PDMS-COOH-CG) that can quickly self-heal at room temperature. The thermal conductivity of PDMS-COOH-CG10 with 10% of graphene content is 0.48 W·m~(-1)·K~(-1), which is 16 times that of PDMS-COOH(0.03 W·m~(-1)·K~(-1)). At room temperature, self-healing efficiency of PDMS-COOHCG10 based on tensile strength can be 53.8% for 30 s and 84.6% for 24 h. Dynamic infrared thermal imaging dipicted that after 2 min of selfhealing at room temperature, the thermal conduction temperature near the damage was basically restored to the level of the pristine sample.     

Multifunctional Thermally Conductive Composite Films Based on Fungal Tree-like Heterostructured Silver Nanowires@Boron Nitride Nanosheets and Aramid Nanofibers

Thermal conduction for electronic equipment has grown in importance in light of the burgeoning of 5G communication. It is imperatively desired to design highly thermally conductive fillers and polymer composite films with prominent Joule heating characteristics and extensive mechanical properties. In this work, “solvothermal & in situ growth” method is carried out to prepare “Fungal tree”-like hetero-structured silver nanowires@boron nitride nanosheet (AgNWs@BNNS) thermally conductive fillers. The thermally conductive AgNWs@BNNS/ANF composite films are obtained by the method of “suction filtration self-assembly and hot-pressing”. When the mass fraction of AgNWs@BNNS is 50 wt%, AgNWs@BNNS/ANF composite film presents the optimal thermal conductivity coefficient of 9.44 W/(m ⋅ K) and excellent tensile strength of 136.6 MPa, good temperature-voltage response characteristics, superior electrical stability and reliability, which promise a wide application potential in 5G electronic devices.     

Enhanced thermal conductivity and mechanical properties of polymeric composites through formation of covalent bonds between boron nitride and rubber chains

Hexagonal boron nitride (BN) platelets, also known as white graphite, are often used to improve the thermal conductivities of polymeric matrices. Due to the poor interfacial compatibility between BN platelets and polymeric matrices, in this study, polyrhodanine (PRd) was used to modify BN platelets and prepared functionalized BN-PRd platelets, thereby enhancing the interfacial interaction between the thermal conductive filler and polymeric matrix. Then, BN-PRd platelets were dispersed into the nitrile butadiene rubber (NBR) matrix to yield high thermally conductive composites. The presence of N? C═S groups in PRd allowed the combination of PRd and NBR chains containing stable covalent bonds via vulcanization reaction. The thermal conductivity of the as-prepared 30 vol% BN-PRd/NBR composite reached 0.40 W/mK, representing an increment of 135% over pure NBR (0.17 W/mK). In addition, the largest tensile strength of NBR composite containing 30 vol% BN-PRd platelets was 880% times of pure NBR. The 30 vol% BN-PRd/NBR composite also displayed a relatively high dielectric constant (9.35 at 100 Hz) and a low dielectric loss tangent value (0.07 at 100 Hz), indicating their usefulness as dielectric flexible materials of microelectronics. In sum, the simplicity and good efficiency of formation of covalent bonds between boron nitride and rubber chains look very promising for large-scale industrial production of high thermally conductive composites.     

高导热氮化硼/芳纶沉析复合薄膜的制备及性能

利用多巴胺(DA)的氧化自聚合特性, 对六方氮化硼(h-BN)进行表面修饰, 并以多巴胺改性后的氮化硼(h-BN@PDA)为导热填料, 对基体芳纶沉析纤维(AF)进行填充, 通过真空辅助抽滤法制备多巴胺改性氮化硼/芳纶沉析(h-BN@PDA/AF)复合薄膜, 并对其微观形貌、 表面官能团、 导热性能、 绝缘性能及力学性能进行研究. 结果表明, 聚多巴胺(PDA)包覆在h-BN表面, 并引入活性基团, 与AF纤维产生氢键, 改善了两者的界面结合, 显著提高了复合薄膜导热性能及绝缘性能. 当h-BN@PDA含量为70%时, h-BN@PDA/AF复合薄膜的导热系数为1.36 W/(m·K), 与纯芳纶沉析薄膜相比, 导热系数的增幅约为697.65%, 体积电阻率为5.96×10 ¹⁴ Ω·m, 拉伸模量高达287.19 MPa.     

Bubble-templated Construction of Three-dimensional Ceramic Network for Enhanced Thermal Conductivity of Silicone Rubber Composites

With the continuous development of the electronics industry, the energy density of modern electronic devices increases constantly,thus releasing a lot of heat during operation. Modern electronic devices take higher and higher request to the thermal interface materials.Achieving high thermal conductivity needs to establish an interconnecting thermal conductivity network in the matrix. For this purpose, the suspension of Al_2 O_3 and curdlan was first foamed to construct a bubble-templated continuous ceramic framework. Owing to the rapid gelation property of curdlan, we can easily remove moisture by hot air drying. Finally, the high thermally conductive composites are prepared by vacuum impregnation of silicone rubber. The result showed that composites prepared by our method have higher thermal conductivity than the samples obtained by traditional method. The thermal conductivity of the prepared composite material reached 1.253 W·m~(–1)·K~(–1) when the alumina content was 69.6 wt%. This facile method is expected to be applied to the preparation of high-performance thermal interface materials.     

Electric-Field-Induced Alignment of Functionalized Carbon Nanotubes Inside Thermally Conductive Liquid Crystalline Polyimide Composite Films

The positive liquid crystals, 4′-heptyl-4-biphenylcarbonitrile (7CB), are used to functionalize carbon nanotubes (LC-CNT), which can be aligned in the liquid crystalline polyimide (LC-PI) matrix under an alternating electric field to fabricate the thermally conductive LC-CNT/LC-PI composite films. The efficient establishment of thermal conduction pathways in thermally conductive LC-CNT/LC-PI composite films with a low amount of LC-CNT is achieved through the oriented alignment of LC-CNT within the LC-PI matrix. When the mass fraction of LC-CNT is 15 wt %, the in-plane thermal conductivity coefficient (λ_∥) and the through-plane thermal conductivity coefficient (λ_⊥) of the LC-CNT/LC-PI composite films reach 4.02 W/(m ⋅ K) and 0.55 W/(m⋅K), which are 90.5 % and 71.9 % higher than those of the intrinsically thermally conductive LC-PI films respectively, also 28.8 % and 5.8 % higher than those of the CNT/LC-PI composite films respectively. Meanwhile, the thermally conductive LC-CNT/LC-PI composite films also possess excellent mechanical and heat resistance properties. The Young's modulus and the heat resistance index are 2.3 GPa and 297.7 °C, respectively, which are higher than the intrinsically thermally conductive LC-PI films and the thermally conductive CNT/LC-PI composite films under the same amount of CNT.     

Mechanically robust,ion-conductive,self-healing glassy hybrid materials via tailored Zn/imidazole interaction

Simultaneously achieving mechanical properties and rapid self-healing under ambient conditions is challenging because of slow diffusion dynamics. Here, we report the design of self-healing hybrids composed of low molecular mass multifunctional silsesquioxane nanoparticles with cross-linked networks formed from non-covalent metal–ligand interactions to address this challenge. Carefully tuning the bond dynamics and strength by changing the counterions and metal–ligand feed ratio enables rapid self-healing and robust mechanical properties (tensile strength = 14.9 MPa and elongation at break = 4.36%) with ion conductivity. Static tensile behavior and rheological response of hybrids revealed dynamic interactions. The hybrids without entanglement can heal from a physical cut at room temperature with a healing efficiency of approximately 90%. This molecular design strategy provides a versatile pathway for the production of self-healing hybrid materials with excellent mechanical properties.     

Enhancement of thermal conductivity and tensile strength of liquid silicone rubber by three-dimensional alumina network

ABSTRACT

Rapidly increasing demands for higher integration density and stability of electronic devices embrace higher requirements for thermally conductive silicone rubber, which is promisingly used in ultra-thin components. In this work, alumina whiskers (AWs) and alumina flakes (AFs) are used to modify liquid silicone rubber (LSR) by fabricating binary (AFs/LSR) or ternary (AWs/AFs/LSR) composites. The thermal conductivity and mechanical strength of the binary and ternary composites were investigated. Thermal conductivity of the binary AFs/LSR composite (25AFs/LSR) was 0.1990 W m^?1 K^?1, while the thermal conductivity of the ternary AFs/AWs/LSR composite (20AFs/5AWs/LSR) was 0.2655 W m^?1 K^?1. Furthermore, the tensile strength of the ternary AWs/AFs/LSR composites increased by 180.9% as compared with the binary system, increased to 7.81 MPa from 2.78 MPa due to the introduction of 1 wt% AWs. As a reason, a significant synergistic effect of AWs and AFs in the enhancement of both thermal and mechanical properties of the LSR was proved. Furthermore, the dielectric property measurements demonstrated that the ternary composites exhibited a lower dielectric constant and dielectric loss, indicating that the AWs/AFs/LSR composites were qualified to be applied in the field of electronic devices.     

聚苯胺／聚乙烯醇导电复合膜的制备及性质研究

用较简单的化学氧化现场吸附聚合法（ｉｎ－ｓｉｔｕｐｏｌｙｍｅｒｉｚａｔｉｏｎ）制得了聚苯胺（ＰＡｎ）／聚乙烯醇（ＰＶＡ）导电复合膜．该膜具有较好的导电性和机械性能；其电导率可达５．８ｓ／ｃｍ，拉伸强度达１３ＭＰａ，断裂伸长率为１１０％左右．本文讨论了制备的各种条件对复合膜导电性能及力学性能的影响、稳定性及电化学活性；并采用循环伏安曲线、扫描电镜（ＳＥＭ）、ＦＴＩＲ谱及元素分析对该复合膜的结构和性能进行了表征．     

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。