石墨烯/聚苯胺复合材料的电磁屏蔽性能

采用直流电弧放电法制备高结晶性石墨烯, 利用乙醇助溶分散法得到石墨烯/聚苯胺电磁屏蔽复合材料, 研究不同掺杂比例的石墨烯/聚苯胺复合材料的电磁屏蔽性能。拉曼光谱分析表明: 由于石墨烯与聚苯胺之间的相互作用, 复合材料中聚苯胺特征峰比纯聚苯胺特征峰稍弱或向低频方向移动。复合物的电导率随石墨烯掺杂量的增加而增大, 当掺杂质量分数为25%时, 其电导率达到19.4 S/cm, 接近纯石墨烯电导率(20.1 S/cm)。频率为2~18 GHz时, 复合材料的电磁屏蔽效能随着石墨烯掺杂量和频率的增大而增强; 当石墨烯掺杂质量分数为25%时, 总屏蔽效能在2~18 GHz范围内由19.8 dB增至34.2 dB, 增加了约42%, 其中吸收部分占总屏蔽效能的比例为66%~81%, 这表明石墨烯/聚苯胺复合材料的电磁屏蔽性质是以电磁波吸收为主; 同时也说明了拥有特殊结构与特性的石墨烯是一种较好的聚苯胺填料, 在微波屏蔽与微波吸收领域将会有广阔的应用前景。     

Electromagnetic interference shielding behavior of poly(trimethylene terephthalate)/multi-walled carbon nanotube composites

Poly(trimethylene terephthalate) [PTT]/multiwalled carbon nanotube [MWCNT] composites having varying amounts of MWCNTs were fabricated with an aim to investigate the potential of such composites as an effective light weight electromagnetic interference (EMI) shielding material in the frequency range of 12.4-18 GHz (Ku-band). PTT/MWCNT composite with shielding effectiveness (SE) of 36-42 dB was obtained at 10% (w/w) MWCNT loading. Shielding mechanism was studied by resolving the total SE into absorption (SE_A) and reflection loss (SE_R). PTT/MWCNT composite showed absorption dominated shielding; thus it can be used as microwave, radar absorbing and stealth material. The effect of MWCNT loadings on electrical conductivity (σ) and dielectric properties of PTT and the correlation among conductivity, tan δ, absorption loss and reflection loss were also studied.     

单壁碳纳米管无纺布/环氧树脂复合材料的电磁屏蔽性能

采用一种导电材料预制体-单壁碳纳米管(Single-wall carbon nanotube,SWCNT)无纺布与环氧树脂复合制备了电磁屏蔽复合材料,并对所制复合材料的电磁屏蔽性能进行了表征。结果表明:所制复合材料对电磁波的屏蔽效率随SWCNT无纺布厚度的增加而增加。在较低的SWCNT无纺布填加量下所制复合材料可以实现对低频电磁波较高的屏蔽效率。不同于填加粉体导电材料所制电磁屏蔽复合材料,作为导电材料预制体使用的SWCNT无纺布是一个独立的整体导电薄膜,可以直接引入到基体当中,不存在分散问题。并且通过简单的导电预制体多层叠加的方式即可实现复合材料更高的屏蔽效率。     

Synthesis of polyaniline/multi-walled carbon nanotube nanocomposites in water/oil microemulsion

A water/oil microemulsion system having been successfully used for synthesizing polyaniline(PANi) nanoparticles, was employed for preparing PANi/multi-walled carbon nanotube (MWCNT) nanocomposites via in situ chemical oxidative polymerization. The structures and the electrical property of PANi/MWCNT nanocomposites were also studied. The studies showed that PANi could coat MWCNTs to form nanocables with core-shell structure, and the backbone structure of PANi was not damaged by the introduction of MWCNTs. The conductivities of PANi/MWCNT nanocomposites were higher than that of PANi. Moreover, a model was supposed to be used for describing a PANi/MWCNT nanocable formation by in situ microemulsion polymerization.     

Synthesis and characterization of externally doped sulfonated polyaniline/multi-walled carbon nanotube composites

Composites of carbon nanotubes with attached carboxylic groups (c-MWCNTs) and water-soluble externally doped sulfonated polyaniline (ED-SPANI) were prepared by solution mixing of c-MWCNT and ED-SPANI aqueous colloids. Fourier-transform infrared spectroscopy, Raman spectroscopy, ultraviolet–visible (UV–Vis) absorption spectroscopy, field-emission scanning and high-resolution transmission electron microscopy were used to characterize their structure and morphology. Raman and UV–Vis spectra revealed the presence of electrostatic interaction between the C–N⁺ species of the ED-SPANI and the COO⁻ species of the c-MWCNTs. The addition of c-MWCNT to ED-SPANI can improve its thermal stability. The conductivity of 3 wt.% ED-SPANI/c-MWCNT composites at room temperature is sixteen times higher than that of ED-SPANI. These results demonstrate that the addition of a small number of c-MWCNTs to an ED-SPANI matrix can form a conducting network in well dispersed composites, thus increasing their electrical conductivity.     

3D打印制备碳纳米管/环氧树脂电磁屏蔽复合材料

采用3D打印技术制备具有连续通孔的环氧树脂基体,利用浸渍工艺将碳纳米管（CNTs）附着于环氧树脂基体孔壁,获得具有优异电性能和电磁屏蔽功能的CNTs/环氧树脂复合材料。研究结果表明,CNTs含量仅为2.86vol%时,CNTs/环氧树脂复合材料电导率高达35 S/m,总电磁屏蔽效能高达39.2 dB（厚度为2.0 mm）。研究表明,CNTs/环氧树脂复合材料对进入其内部电磁波的吸收占总屏蔽效能的98%,表现出吸收屏蔽为主导的电磁屏蔽机制。CNTs/环氧树脂复合材料的弯曲强度和弯曲模量相比环氧树脂基体也有一定的提高。该研究为具有优异电磁屏蔽性能的高分子基复合材料制备提供了新思路和方法。      

Composite of DGEBA/TBA epoxy blend and amine-functionalized carbon nanotube: Structural,thermal, nonflammability,and EMI shielding studies

Novel blend of diglycidyl ether of bisphenol-A (DGEBA) and tetrabromo bisphenol-A (TBA) was reinforced with acid-functionalized (MWCNT-F) and amine-functionalized multi-walled carbon nanotube (MWCNT-A). DGEBA/MWCNT-A displayed fine tubular morphology with open nanotube ends, while DGEBA/TBA/MWCNT-A displayed somewhat aggregated morphology due to lesser filler content. DGEBA/TBA/MWCNT-A system showed maximum enhancement in decomposition temperature (T₀ = 404°C, T_max = 583°C). Glass transition temperature and Limiting oxygen index of DGEBA/TBA/MWCNT-A were also higher (221°C and 55%) compared with other systems. DGEBA/TBA/CNT-A 0.1 had crystalline morphology with diffractions at 12.7° and 26.09°. Novel nanocomposite revealed EMI shielding effectiveness of ～15.05–15.18 dB, i.e., suitable for aerospace applications.     

原位聚合法制备铁氧体/聚苯胺吸波复合材料的研究进展

电磁污染已成为继空气污染、水污染和噪声污染之后的第四大污染, 吸波材料因其吸收和衰减特性, 可以作为解决电磁污染的有效手段。聚苯胺(PANI)作为一种电阻损耗型吸波材料, 可以满足吸波材料"厚度薄"、"质量轻"的发展理念, 但由于阻抗匹配度差, 吸波性能并不理想。铁氧体作为一类传统的磁损耗型吸波材料, 因其密度较高使其适用范围受到限制。高密度的铁氧体与低密度的聚苯胺复合制备的吸波材料, 不仅可以调整复合材料的密度, 而且还能改善复合材料的阻抗匹配, 提高铁氧体/聚苯胺复合材料的吸波性能。本文首先探讨了聚苯胺以及铁氧体/聚苯胺复合材料的制备方法, 其次阐述了铁氧体/聚苯胺复合材料的吸波机理。然后分别归纳了尖晶石型、磁铅石型、石榴石型铁氧体与聚苯胺制备的复合材料在吸波领域的研究进展。最后指出铁氧体/聚苯胺复合材料应趋向于电磁仿真和多元复合化的方向发展。     

Scalable Fabrication of Nacre-Structured Graphene/Polytetrafluoroethylene Films for Outstanding EMI Shielding Under Extreme Environment

In this work, inspired by the great advantage of the unique “brick-mortar” layered structure as electromagnetic interference (EMI) shielding materials, a multifunctional flexible graphene nanosheets (GNS)/polytetrafluoroethylene (PTFE) composite film with excellent EMI shielding effects, impressive Joule heating performance, and light-to-heat conversion efficiency is fabricated based on the self-emulsifying process of PTFE. Both PTFE microspheres and nanofibers are employed together for the first time as “sand and cement” to build unique nacre-structured EMI shielding materials. Such configuration can obviously enhance the adhesion of composites and improve their mechanical property for the application under extreme environment. Moreover, the simple and effective repetitive roll pressing method can be used for the scalable production in industrialization. The GNS/PTFE composite film shows a high EMI shielding effectiveness (SE) of 50.85 dB. Furthermore, it has a high thermal conductivity of 16.54 W (m K)⁻¹, good flexibility, and recyclable properties. The excellent fire-resistant and hydrophobic properties of GNS/PTFE film also ensure its reliability and safety in practical application. In conclusion, the GNS/PTFE film demonstrates the potential for industrial manufacturing, and outstanding EMI shielding performance with high stability and durability, which has a broad application prospect for electronic devices in practical extreme outdoor environments.     

Aerosol based fabrication of a Cu/polymer and its application for electromagnetic interference shielding

The effect of a catalytic surface activation on the electromagnetic interference shielding of Cu deposited polymer substrates was investigated. The surface of polymer substrates was catalytically activated by different methods respectively adopted Pd aerosol nanoparticles and Sn-Pd wet chemical processes. Although both activations initiated the deposition of Cu on the substrates, differences such as morphology (Pd aerosol: ~80 nm vs Sn-Pd: ~ 140 nm, in Cu grain size) and composition (Pd aerosol: Cu and Pd vs Sn-Pd: Cu, Pd, Sn, and Cl) of Cu deposits were presented. Specimens activated using Pd aerosol nanoparticles showed a higher range of shielding effectiveness by about 4-10 dB than those activated by Sn-Pd processes in 2-18 Ghz frequencies.     

The manufacture and investigation of multi-walled carbon nanotube/polypyrrole/EVA nano-polymeric composites for electromagnetic interference shielding

In this study, the multi-walled carbon nanotube (MWNT)-polypyrrole (PPy) was synthesized by chemical oxidative polymerization using cetyltrimethylammonium bromide (CTAB) as the cationic surfactant. The high electric conductivity of the MWNT-PPy(Cl⁻) was affirmed by the measurement of 4-point-probe method. Then, the MWNT-PPy(Cl⁻) was used as conductive fillers and was compounded with ethylene-vinyl acetate (EVA) by blending to form polymeric composite (MWNT-PPy(Cl⁻)/EVA) that possesses excellent electromagnetic interference shielding (EMI SE). Because of the high conductivity of the MWNT-PPy(Cl⁻) (29/71 wt.%), the MWNT-PPy(Cl⁻) would interdict the conductive network in the composites. This polymeric composite material could shield the electromagnetic wave. As the cationic surfactant CTAB was added in the MWNT-PPy(Cl⁻) chemical oxidative polymerization process, the effect of the surfactant was dispersed, absorbed and attenuated on the MWNT in the chemical oxidative polymerization. For this reason, the EMI SE of the MWNT-PPy(Cl⁻)/EVA composites had an obvious improvement from 10-15 dB to 45-55 dB. In this investigation, the optimum conductive filler was 75.0 phr PPy(Cl⁻) coated on 18.0 phr MWNT. The morphology of the composite also presented a uniform conducting network when a lot of MWNT-PPy(Cl⁻) was added.     

Li4Ti5O12-聚苯胺复合材料的制备与电化学性能

以醋酸锂和钛酸四丁酯为原料，以乙醇为溶剂，采用溶胶．凝胶法制备Li4Ti5O12；以苯胺、过硫酸铵为原料，以盐酸为溶剂，采用原位聚合法合成Li4Ti5O12-聚苯胺复合材料。采用x射线衍射、红外光谱和电化学测试等对复合材料进行了表征。结果表明，聚苯胺的加入明显提高了Li4Ti5O12的电子导电性能，Li4rri5O12-PAn复合材料具有比Li4Ti5O12更好的高倍率性能和循环稳定性。0.1C和2.0C放电时Li4Ti5O12-PAn的放电容量达到了191．3和148．9mAh．g^-1，经80次循环后二者平均每次循环容量衰减率分别为0．13％和0．61％。     

Synthesis of MnO2/short multi-walled carbon nanotube nanocomposite for supercapacitors

Multi-walled carbon nanotubes (MWNTs) were selectively etched in molten nitrate to produce short MWNTs (s-MWNTs). MnO₂/s-MWNT nanocomposite was synthesized by a reduction of potassium permanganate under microwave irradiation. For comparative purpose, MnO₂/MWNT nanocomposite was also synthesized and investigated for its physical and electrochemical performance. Uniform and conformal MnO₂ coatings were more easily formed on the surfaces of individual s-MWNTs. MnO₂/s-MWNT nanocomposite estimated by cyclic voltammetry (CV) in 0.5 M Na₂SO₄ aqueous solution had the specific capacitance as high as 392.1 F g⁻¹ at 2 mV s⁻¹. This value was more than 48.9% larger than MnO₂/s-MWNT nanocomposite. In addition, MnO₂/s-MWNT nanocomposite was also examined by repeating the CV test at a scan rate of 50 mV s⁻¹, exhibiting an excellent cycling stability along with 99.2% specific capacitance retained after 1000 cycles. Therefore, MnO₂/s-MWNT nanocomposite is a promising electrode material in the supercapacitors.     

Polymer/carbon based composites as electromagnetic interference (EMI) shielding materials

The extensive development of electronic systems and telecommunications has lead to major concerns regarding electromagnetic pollution. Motivated by environmental questions and by a wide variety of applications, the quest for materials with high efficiency to mitigate electromagnetic interferences (EMI) pollution has become a mainstream field of research. This paper reviews the state-of-the-art research in the design and characterization of polymer/carbon based composites as EMI shielding materials. After a brief introduction, in Section 1, the electromagnetic theory will be briefly discussed in Section 2 setting the foundations of the strategies to be employed to design efficient EMI shielding materials. These materials will be classified in the next section by the type of carbon fillers, involving carbon black, carbon fiber, carbon nanotubes and graphene. The importance of the dispersion method into the polymer matrix (melt-blending, solution processing, etc.) on the final material properties will be discussed. The combination of carbon fillers with other constituents such as metallic nanoparticles or conductive polymers will be the topic of Section 4. The final section will address advanced complex architectures that are currently studied to improve the performances of EMI materials and, in some cases, to impart additional properties such as thermal management and mechanical resistance. In all these studies, we will discuss the efficiency of the composites/devices to absorb and/or reflect the EMI radiation.     

功能化碳纳米管的制备及功能化碳纳米管/尼龙6复合纤维

采用多聚磷酸(PPA)/P₂O₅弱酸体系, 通过傅克反应(Friedel-Crafts reaction)对多壁碳纳米管(MWCNTs)进行功能化改性, 加入己内酰胺后采用原位聚合法制备功能化碳纳米管(F-MWCNTs)/尼龙6(PA6)复合材料, 并熔融纺丝制备复合纤维。通过TEM、TG、DSC、SEM及力学性能测试对复合纤维进行表征。结果表明: 在MWCNTs表面成功地接枝了氨基, F-MWCNTs均匀地分散在PA6基体中, 没有发生团聚现象, 并且与基体具有很好的界面作用; F-MWCNTs的加入, 对复合纤维的熔融温度和结晶度影响不大, 结晶温度有所提高, 并明显提高了复合纤维的热稳定性; 随着F-MWCNTs的加入, 复合纤维的拉伸断裂强度和杨氏模量增加, 当F-MWCNTs质量分数为0.5%时, 拉伸断裂强度和杨氏模量达到最大, 比纯PA6纤维分别提高了45%和208%。     

Hydrothermal synthesis of titanate nanoparticle/carbon nanotube hybridized material for dye sensitized solar cell application

With the hydrothermal treatment, titanate nanostructure with distinctively different morphology and surface characteristics was successfully synthesized from commercial rutile titania powder dispersed in accommodating media which were deionized water or NaOH solution. Hybridized materials of titanate nanoparticles and carbon nanotubes (CNT) were also synthesized by the hydrothermal treatment process. Intrinsic interaction of titanate nanoparticles and CNTs could be confirmed by spectroscopic analysis. The synthesized titanate nanoparticle/CNT hybridized material was then employed for fabricating a working electrode of dye-sensitized solar cells (DSSC). Based on experimental results, DSSC fabricated from the hybridized titanate nanoparticles and carbon nanotubes could provide the highest photoconversion efficiency of approximately 3.92%.     

硫醇@三聚氰胺甲醛树脂/环氧树脂固化剂的制备及性能表征

采用三聚氰胺-甲醛树脂(PMF)为壁材,三羟甲基丙烷三(3-巯基丙酸酯)(TMPMP)作为芯材,原位乳液聚合法制备了硫醇@三聚氰胺甲醛树脂(TMPMP@PMF)微胶囊固化剂。研究了乳化剂种类及用量,囊壁质量比,反应温度,反应时间,pH值对合成TMPMP@PMF微胶囊粒径及稳定性等影响。结果表明:当反应乳液中芯材的质量分数达到2wt%,同时芯材与壁材的单体质量比达到2∶1时,能制备出粒径在大约100μm,粒径均匀的TMPMP@PMF微胶囊。TMPMP@PMF微胶囊的结构稳定,耐热性好,并且呈闭孔结构。采用TMPMP@PMF微胶囊为固化剂,与环氧树脂(EP)基体混合配制成压敏型TMPMP@PMF/EP固化剂,发现微胶囊结构在受到外力作用时能及时破裂,室温甚至低温下都能短时间使环氧树脂固化,并且能够很好地改善固化剂的抗冲击性能。     

Synthesis of poly(3-hexylthiophene)-graft-poly(t-butyl acrylate-co-acrylic acid) and its role of compatibilizer for enhancement of mechanical and electrical properties of Nylon 66/multi-walled carbon nanotube composites

A compatibilizer, poly(3-hexylthiophene)-graft-poly(t-butyl acrylate-co-acrylic acid) was synthesized, where the acrylic aid was formed by hydrolysis of t-butyl acrylate unit. It has been identified that poly(3-hexylthiophene) backbone of the compatibilizer interacts with multi-walled carbon nanotubes (MWCNTs) via π–π interaction and the acrylic acid unit of the graft chain interacts with Nylon 66 (N66) matrix via hydrogen bonding. When a small amount of compatibilizer was added to N66/MWCNT composites, MWCNTs were more homogeneously dispersed in N66 matrix than the case without compatibilizer. As a consequence, mechanical and electrical properties of the composites with compatibilizer were largely improved as compared with those of composites without compatibilizer.