Synthesis,characterization and supercapacitors of electrically conductive PPy/graphene/rare earth ions composites

PPy/graphene/rare earth ions (PPy/GR/RE³⁺) were prepared using an in situ chemical polymerization of the monomer in the presence of FeCl₃ oxidant and p-toluenesulfonic acid dopant. The PPy/GR/RE³⁺ composites were characterized by FT-IR spectroscopy, four-point probe conductivity, scanning electron microscopy and transmission electron microscopy. The maximum conductivity of PPy/GR/Gd³⁺ composites is about 9.71 S/cm found with 1 wt% GR and 2 wt% Gd³⁺ at room temperature. The capacitance of the composite electrodes was investigated with cyclic voltammetry. As results of this study, the PPy/GR/Gd³⁺ was effective to obtain fully reversible and very fast faradaic reaction. Hence, the PPy/GR/Gd³⁺ could contribute to the pseudo-capacitive charge storage. The PPy/GR/Gd³⁺ exhibited higher specific capacitance of ~238 F/g at 1 A/g current density. Thermal gravimetric analysis demonstrates an improved thermal stability of PPy in the PPy/GR/Gd³⁺ composites.     

纳米石墨片/环氧树脂复合材料的制备及性能

分别采用低温固化剂和高温固化剂制备了纳米石墨片/环氧树脂复合材料。通过电阻测试仪和材料试验机研究了纳米石墨片的含量对复合材料导电性能和力学性能的影响规律,并将溶液混合法与直接混合法制备的复合材料的性能进行对比,同时比较了纳米复合材料的性能与微粉石墨/环氧树脂复合材料的性能。结果表明,溶液混合法制备的复合材料逾渗阈值更低,可得到填料质量分数达60%、体积电阻率为0.0085 Ω·cm的纳米复合材料。当填料质量分数高于4%时,纳米复合材料的力学性能低于微粉复合材料。     

One‐step synthesis of highly conductive PPy/graphite nanosheets/Gd3+ composites

Highly conductive polypyrrole/graphite nanosheets/Gd³⁺ (PPy/nanoG/Gd³⁺) composites are fabricated via in situ polymerization using p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The effects of the graphite nanosheets and Gd³⁺ loading on the electrical conductivity are investigated. The maximum conductivity of PPy/nanoG/Gd³⁺ composites about 17.86 S/cm found with 3 wt% graphite nanosheets and 6 wt% Gd³⁺ at room temperature. The results showed that the high‐aspect‐ratio structure of graphite nanosheets played an important role in forming a conducting network in PPy matrix. Thermal gravimetric analysis demonstrates an improved thermal stability of PPy in the PPy/nanoG/Gd³⁺ composites. The microstructures of PPy/nanoG/Gd³⁺ are evidenced by the SEM and TEM examinations. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

聚合物/纳米石墨微片复合材料的研究进展

详述了纳米石墨微片（NanoG）的制备工艺、结构特征,重点归纳总结了纳米石墨微片与聚甲基丙烯酸甲酯（PMMA）、聚苯胺(PANI)、聚苯乙烯(PS)以及聚吡咯(PPy)复合材料的复合方法、性能及应用情况。最后对聚合物/纳米石墨微片复合物制备工艺问题,纳米石墨微片在聚合物中的分散性问题以及如何提高聚合物/纳米石墨微片复合物的导电性问题进行了展望,同时提出改性的纳米石墨微片与聚合物复合的应用研究将是一个崭新的研究领域。     

Preparation and characterization of branched polyesteramide/mix rare earth oxides composites

Branched polyester amide containing various amount of mix rare earth oxides (RE₂O₃) were synthesized by in-situ solution condensation of AB₂ monomer synthesized based on the reaction between maleic anhydride and diethanolamine (DEA). The effect of AB₂ monomer self-polycondensation on the RE₂O₃ surface and the properties of synthesized composites were investigated by using Fourier-transform infrared spectra (FT-IR), ultraviolet–visible absorption spectra (UV–vis), X-ray photoelectron spectroscopy, scanning electron microscopy, thermogravimetric analysis and viscosity determination. AB₂ monomer can envelop RE₂O₃ particles as an organic matrix (HBPEA′) by self-polycondensation under the proposed condition. Ionization of surface of RE₂O₃ aggregates can result in the rare earth ionic (RE³⁺) and the resulting RE³⁺ might coordinate with the organic matrix. Thermal stability of branched polyesteramide can be significantly improved in presence of 5 wt% RE₂O₃, possibly due to the coordination reaction between RE₂O₃ and the active group of the organic matrix.     

Preparation and characterization of polysulfone/graphite nanosheets composites capsules for the adsorption of phenol in aqueous solution

In this study, the polysulfone (PSF) capsules containing graphite nanosheets (GNS) were successfully prepared by a phase inversion precipitation method. Scanning electron microscopy and thermogravimetry were employed in the characterization of the as‐prepared PSF/GNS composites capsules. Meanwhile, the adsorption properties of the composites capsules for the phenol in aqueous solution were investigated by batch methods. The results showed that the phenol adsorption uptake would be increased with the enhancement of initial concentration and adsorption time, and the adsorption of phenol should be more favorable at pH value less than 9. The composites capsules would be a kind of promising alternative adsorbent with high adsorption capacity for the phenol from aqueous solutions at a low concentration. The adsorption kinetics of the capsules for phenol accorded with pseudo‐second‐order model, and the best fits of adsorption isotherms followed the Freundlich equation. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Synthesis of graphite nanosheets/polyaniline nanorods composites with ultrasonic and conductivity

The graphite nanosheets/polyaniline (GN/PANI) nanorods composites were fabricated via ultrasonic polymerization of aniline monomer in the presence of GN, which was used as electric filling. The kind of doped acids, the concentration, and the contents of the GN were used as impact factors to the conductivity of the materials that were investigated. The structure of nanocomposites were characterized by FTIR and SEM. The results show that ultrasonic can effectively restrain the agglomerate of the aniline and come to uniformity nanorods composites. The conductivity reached to 4.8 S/cm and 22 S/cm, respectively. The thermal stability of GN/PANI nanorods composites is superior to pure PANI as shown by TG analysis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of graphite oxide/polypyrrole composites

Graphite oxide (GO)/polypyrrole (PPy) composites (GPs) and 1,5-naphthalene disulfonic acid (1,5-NDA) doped GPs (1,5-NGPs) have been successfully synthesized via in situ polymerization of pyrrole on GO. The conductivity of 1,5-NGPs is as high as 7 S/cm, seven orders of magnitude higher than that of pristine GO. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show PPy “dressed” on the surface of GO layers, while Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analyses confirm the interaction between GO and PPy. The results of thermogravimetric analysis (TGA) and heat treatment at 1000 °C show that the “dressed” PPy on the surface of GO layers in GPs and 1,5-NGPs has effectively prevented the deflagration of GO.     

稀土/高分子复合材料的射线屏蔽性能和磁性能

综述了稀土／高分子复合材料的射线屏蔽性能和磁性能,指出稀土／高分子复合材料在X射屏蔽应用中可有效地弥补铅的弱吸收区,具有高稀土含量的复合高分子屏蔽材料具有强的热中子吸收能力,含稀土的共聚物具有强顺磁性,提出了制备磁性和磁智能稀土／高分子复合材料的可行性。     

碳纳米管增强环氧／石墨复合材料的制备与性能研究

采用粉末冶金法制备了碳纳米管增强环氧／石墨复合材料,并研究了酸洗处理对复合材料弯曲强度、硬度和导电性能的影响。结果表明：与未处理碳纳米管相比,酸处理的碳纳米管增加了环氧／石墨复合材料的弯曲强度和硬度,降低了电阻率。酸处理的碳纳米管增强环氧／石墨复合材料的弯曲强度达到21．9MPa,比未添加碳纳米管时提高了近22％;同时复合材料的硬度达到最大值21．7HS,比未添加碳纳米管时提高了近10％;复合材料的电阻率达到了最小值45036μΩ·cm,比未添加碳纳米管时复合材料的电阻率降低了近17％。     

石墨烯/δ-MnO2复合材料的制备及其超级电容器性能

采用螯合法制备了RGO/δ-MnO₂复合材料,并用X射线粉末衍射（XRD）、低压氮气吸附脱附（BET）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、能谱（EDS）、热重（TGA）对其结构和物相进行表征。采用循环伏安测试（CV）、恒电流充放电（GCD）以及循环测试对所制材料电化学储能进行测试。结果表明RGO/δ-MnO₂复合材料比纯石墨烯和纯δ-MnO₂具有更优异的电化学性能。当电流密度为1 A·g^-1时,RGO/δ-MnO₂复合材料的比电容可达322.6 F·g^-1,比纯δ-MnO₂电极材料高234.2 F·g^-1,比纯石墨烯高212.1 F·g^-1。当电流密度放大10倍后,RGO/δ-MnO₂复合材料的比电容保留率为79.1%。在1000次恒流充放电测试后,比电容为252 F·g^-1（99.6%）,说明该方法制备的RGO/δ-MnO₂复合材料是一种有应用前景的超级电容器电极材料。     

MOF-derived PPy/carbon-coated copper sulfide ceramic nanocomposite as high-performance electrode for supercapacitor

To obtain a battery-type ceramic electrode material for supercapacitors, we used a metal-organic framework (HKUST-1) as a template to prepare ceramic material Cu₉S₈@C. Firstly, we adopted the calcination–vulcanization method to synthesize Cu₉S₈@C. Then we deposited it onto a carbon fiber cloth and employed it. Moreover, polypyrrole PPy/Cu₉S₈@C-CC nanocomposite electrodes were prepared via electrochemical deposition. By means of high-temperature calcination and vulcanization, the copper atoms of HKUST-1 were successfully transformed into Cu₉S₈ nanoparticles, and the organic ligand was carbonized into amorphous carbon in Cu₉S₈@C. The results showed that the PPy/Cu₉S₈@C-CC electrode presented a specific capacitance of 270.72F/g at a scan speed of 10 mV/s in a 1 M KCL aqueous solution. This value was much higher than that of Cu₉S₈@C-CC and Cu₉S₈-CC electrodes, as confirmed by the results of electrochemical test. At a scan rate of 10 mV/s, the capacitance retention rate for PPy/Cu₉S₈@C-CC after 3000 cycles was 80.36%, indicating its superior cycle characteristics. Moreover, PPy/Cu₉S₈@C-CC exhibited good frequency response. These results indicate that PPy/Cu₉S₈@C is an ideal electrode material for energy storage and conversion applications.     

Preparation and characterization of graphite nanosheets from ultrasonic powdering technique

Natural flake graphite was exfoliated into exfoliated graphite via an acid intercalation procedure. The resulting exfoliated graphite was a worm-like particle composed of graphite sheets with thickness in the nanometer scale. Subjecting it to ultrasonic irradiation, the exfoliated graphite was effectively further foliated into isolated graphite nanosheets. SEM, TEM, SAD, laser counting, and BET measurements revealed that the graphite nanosheets prepared with 10 h irradiation were about 52 nm in thickness and 13 μm in diameter. FTIR examination showed that there were oxygen-containing groups presented on the surface of the exfoliated graphite. This result substantiated the statement reported in the literature that acid treatment could result in oxidization of carbon bonds on graphite surface.     

Preparation and thermal conductivity of novolac/Ni/graphite nanosheet composites

A high thermal conductivity novolac/nickel/graphite nanosheet (novolac/Ni/NanoG) composite was synthesized through in situ polymerization. Graphite nanosheet (NanoG) was prepared by sonicating expanded graphite (EG) in an aqueous alcohol solution and was plated with nickel through an electrodeposition method. The X‐ray diffraction spectrum shows that nickel was successfully plated onto the graphite surface and the nickel thickness is about 27.89 nm. The microstructures of the Ni/NanoG were characterized by scanning electron microscopy and transmission electron microscopy. The results reveal that nickel particles with the average diameter of 25 nm are coated on NanoG surface homogeneously and densely. Energy dispersive spectrometry spectrum confirms that the Ni content coated on NanoG surface, whose atomic percentage is 61%, is much higher than that of C element. The values predicted by theoretical model were underestimated the thermal conductivity of novolac/Ni/NanoG composites. Among NG, EG, NanoG, and Ni/NanoG four kinds of particles, the Ni/NanoG improved the thermal conductivity of novolac resin significantly. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and structure of rare earth/thermoplastic polyurethane fiber for X-ray shielding

Rare earth/polypropylene (PP)/thermoplastic polyurethane (TPU) fibers were prepared by melting spinning with different mass ratios of PP to TPU. Then the rare earth/TPU shielding fiber was obtained by removing the PP matrix phase from the blend fiber using xylene. The fibers were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analyzer (TG), and scanning electron microscopy (SEM). Short fibers were compression-molded for the test of lead equivalent. The results showed that the lead equivalent of the rare earth/TPU composite fibers was 0.19 mmPb when the mass ratio of PP/TPU increased to 60/40. At this mass ratio, the X-ray shielding performance of the fiber was the best. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47435.     

石墨/TinO2n-1复合材料的制备及性能

在常压下,以钛白粉为原料,石墨为还原剂,采用碳热还原法制备了石墨/Ti_nO_2n-1复合材料。采用XRD系统分析了碳热还原过程中钛的价态变化规律;采用XPS、SEM、TEM分析了特定样品的形貌、结构和元素组成。XRD分析结果表明,控制不同的还原条件,可以得到不同n值的石墨/Ti_nO_2n-1复合材料,且还原过程的物相转变顺序为：TiO₂（锐钛型）、TiO₂（金红石型）、Ti₉O₁₇、Ti₈O₁₅、Ti₆O₁₁、Ti₅O₉和Ti₄O₇。在还原温度为1250℃,还原时间为20min,碳钛比为5∶10的条件下所制备的石墨/Ti_nO_2n-1复合材料的电阻率最低,其值为0.1465Ω·cm。吸附/光降解实验表明,石墨/Ti_nO_2n-1复合材料对亚甲基蓝的吸附能力比纯石墨显著增强,吸附去除率为纯石墨的1.40~3.20倍;石墨/Ti_nO_2n-1复合材料对亚甲基蓝具有光催化降解活性,但是其光降解能力低于锐钛型TiO₂;复合材料的催化降解速率常数最大值为0.0047min^-1。     

镀镍石墨/杜仲橡胶复合材料的制备及性能

用硅烷偶联剂对镀镍石墨(NCG)进行湿法处理,采用机械共混法制备了镀镍石墨/杜仲橡胶(EUG)复合材料,考察了NCG用量对NCG/EUG复合材料导电性能、电磁屏蔽效能和力学性能的影响。结果表明,随着NCG质量分数的增加,NCG/EUG复合材料的电导率和电磁屏蔽效能逐渐增大,拉伸强度先增大后减小,扯断伸长率逐渐降低,邵尔A硬度逐渐增大。当NCG质量分数为50%时,NCG/EUG复合材料的电导率可达到2.59 S/cm,电磁屏蔽效能最高可达到47.50 dB。     

Preparation of iminodiacetic acid-type composite chelating material IDAA-PGMA/SiO2 and preliminary studies on adsorption behavior of heavy metal ions and rare earth ions

A kind of iminodiacetic acid (IDAA)-type composite chelating materials was prepared by first graft polymerization and subsequent polymer reaction. Monomer glycidyl methacrylate (GMA) was grafted on micron-sized silica gel particles in the manner of “graft through” in a solution polymerization system, resulting in the grafted particles poly(glycidyl methacrylate) (PGMA)/silicon dioxide (SiO₂). Subsequently, the ring-opening reaction of the epoxy groups of the grafted PGMA was carried out with IDAA as reaction reagent, resulting in the bonding of IDAA groups onto PGMA/SiO₂ and obtaining the composite chelating material IDAA-PGMA/SiO₂ particles. The effects of the main factors on the graft polymerization of GMA and the bonding reaction of IDAA were examined emphatically, and the adsorption behavior of IDAA-PGMA/SiO₂ particles toward several kinds of heavy metal ions and rare earth ions was preliminarily explored. The experiments results show that: (a) to obtain the grafted particles PGMA/SiO₂ with high grafting degree, in the graft polymerization step, the reaction temperature and the used amount of initiator should be controlled. The suitable temperature is 70°C and the appropriate used amount of initiator is 1.4 % of the monomer mass. Under the optimal conditions, the grafted degree of PGMA can reach 17.50 g/100 g. (b) It is feasible to introducing of IDAA groups onto PGMA/SiO₂ particles via ring-opening reaction of epoxy groups of the grafted PGMA under alkaline conditions, and the bonding rate of IDAA group can get up to 70% based on epoxy groups of the grafted PGMA. (c)The composite chelating material IDAA-PGMA/SiO₂ possesses very strong chelating adsorption ability for heavy metal ions, and especially toward Pb²⁺ ion, the adsorption capacity can reach 24 g/100 g. (d) The adsorption ability of IDAA-PGMA/SiO₂ for rare earth ions is weaker than that for heavy metal ions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚吡咯/有机蒙脱土纳米复合材料的制备及其导电性

以三氯化铁(FeCl3)为氧化剂,对甲苯磺酸钠(TSANa)为掺杂剂,使进入经有机插层剂改性的有机蒙脱土(OMMT)层间的吡咯(Py)发生氧化聚合反应,制备了具有良好导电性的聚吡咯/有机蒙脱土(PPy/OMMT)纳米复合材料。结果表明,采用插层剂为十八烷基三甲基氯化铵(OTAC)改性的有机蒙脱土OMMT-O,FeCl3与Py的摩尔比为2 14,Py与OMMT-O的质量比为0 24,TSANa的浓度为0 023g·ml-1,在20℃反应6h,得到的PPy/OMMT-O纳米复合材料的电导率达到3 07S·cm-1。XRD测试表明,在形成复合材料过程中PPy已经插层进入到蒙脱土的片层中。