Polyimide nanohybrid films with electrochemically functionalized graphene

Graphite was functionalized electrochemically in a potassium fluoride solution and used to prepare polyimide (PI)/graphene nanohybrid films. The as‐made electrochemically fluorinated graphene (EFG) was used to prepare nanohybrid films with colorless PI, which was synthesized from 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride and bis(trifluoromethyl) benzidine by in situ polymerization. The surface functionalization of graphite was characterized by powder XRD, TEM with energy dispersive X‐ray spectroscopy elemental mapping, X‐ray photoelectron spectroscopy, Raman spectroscopy, and TGA. The microstructure of the films was characterized by Fourier transform IR spectroscopy, XRD and SEM. The film properties were measured using a universal testing machine, TGA, dynamic mechanical analysis, four‐point probe, UV–visible spectroscopy and water contact angle analysis. EFG improved the tensile strength and modulus of the nanohybrid films by 20% and 50%, respectively. The glass transition temperature and electrical conductivity of the nanohybrid films were 12 °C and nine orders of magnitude higher than those of the neat PI film, respectively. The nanohybrid film maintained 80% optical transmittance even after the addition of 0.1 wt% EFG. © 2019 Society of Chemical Industry     

Morphological and physical properties of a thermoplastic polyurethane reinforced with functionalized graphene sheet

BACKGROUND: Functionalized graphene sheet (FGS) was recently introduced as a new nano‐sized conductive filler, but little work has yet examined the possibility of using FGS as a nanofiller in the preparation of polymer nanocomposites. In particular, there are currently no published papers that evaluate polyurethane/FGS nanocomposites. The purpose of this study was to prepare a polyurethane/FGS nanocomposite and examine the morphological and physical properties of the material. RESULTS: A cast nanocomposite film was prepared from a mixture of thermoplastic polyurethane (TPU) solution and FGS suspended in methyl ethyl ketone. The FGS dispersed on the nanoscale throughout the TPU matrix and effectively enhanced the conductivity. A nanocomposite containing 2 parts of FGS per 100 parts of TPU had an electrical conductivity of 10^?4 S cm^?1, a 10⁷ times increase over that of pristine TPU. The dynamic mechanical properties showed that the FGS efficiently reinforced the TPU matrix, particularly in the temperature region above the soft segment melt. CONCLUSION: Our results show that FGS has a high affinity for TPU, and it could therefore be used effectively in the preparation of TPU/FGS nanocomposites without any further chemical surface treatment. This indicates that FGS is an effective and convenient new material that could be used for the modification of polyurethane. It could also be used in place of other nano‐sized conductive fillers, such as carbon nanotubes. Copyright © 2009 Society of Chemical Industry     

Kevlar oligomer functionalized graphene for polymer composites

Kevlar oligomer functionalized graphene (FGS) was prepared by simple grafting of amino-terminated Kevlar oligomer on graphene oxide (GO) followed by reducing with hydrazine hydrate. The incorporation of FGS shows pronounced effect on the host polymers. High-level reinforcement of both PMMA and PI is observed with low content of FGS (≤0.2 wt %), in this lower loading range, the tensile modulus and strength of composites increase almost linearly as a function of the adding amount of FGS. But no further improvement is obtained as the content of FGS further increased (>0.2 wt %). The mechanism under the reinforcement effect against the FGS loadings is discussed based on the morphological characterizations of the composites. The thermal properties of the composites were also investigated. The glass transition temperature and thermal stability of PMMA were dramatically increased even with the addition of only a small amount of FGS.     

PS/POE/功能化石墨烯纳米复合材料的制备和性能研究

利用马来酸酐接枝聚烯烃(POE-g-MAH)弹性体为增韧剂,乙二胺功能化石墨烯(G-EDA)为纳米填料,经熔融共混法制备了聚苯乙烯(PS)/POE-g-MAH/G-EDA纳米复合材料,并对填料和所得纳米复合材料的结构和性能进行了全面的表征。红外光谱(FTIR)、扫描电子显微镜(SEM)、力学性能、维卡软化温度和熔融指数测试表明:乙二胺(EDA)已成功接枝于石墨烯的表面上;共混过程中,POE-g-MAH的酐基与EDA的氨基发生反应改善了共混体系的界面相容性;G-EDA在熔融共混过程中均匀分散于PS基体中;随着G-EDA含量的增加,复合材料的拉伸强度先增大后降低,当G-EDA质量分数为0.5%时,复合材料的拉伸强度达到最大值,比PS/POE-g-MAH提高了12.3%,比纯PS提高了15.5%;而当G-EDA质量分数为0.75%时,复合材料的冲击强度达到最大值,比PS/POE-g-MAH提高了22%,比纯PS提高了22.4%。因此,当G-EDA的质量分数在0.5%~0.75%之间时,复合材料的综合力学性能最好。G-EDA的加入,纳米复合材料的邵氏A硬度、维卡软化温度等都逐渐增大,而熔融指数逐渐降低。     

Effect of nitrile functionalized graphene on the properties of poly(arylene ether nitrile) nanocomposites

In this study, novel nitrile functionalized graphene (GN‐nitrile)/poly(arylene ether nitrile) (PEN) nanocomposites were prepared by an easy solution‐casting method and investigated for the effect of surface modification on the dielectric, mechanical and thermal properties. Graphene (GN) was first functionalized by introduction of nitrile groups onto the GN plane, which was confirmed by scanning electron microscopy, differential scanning calorimetry, Fourier transform infrared spectroscopy, thermogravimetric analysis and dispersibility research. Compared with pure GN, the grafted nitrile groups on the GN‐nitrile can interact with nitrile groups in PEN and lead to flat but better dispersion and stronger adhesion in/to the PEN matrix. Consequently, GN‐nitrile had a more significant enhancement effect on the properties of PEN. The dielectric constant of the PEN/GN‐nitrile nanocomposite with 5 wt% GN‐nitrile reaches 11.5 at 100 Hz, which is much larger than that of the pure PEN matrix (3.1). Meanwhile, dielectric loss is quite small and stable and the dielectric properties showed little frequency dependence. For 5 wt% GN‐nitrile reinforced PEN composites, increases of 17.6% in tensile strength, 26.4% in tensile modulus and 21 °C in T_d5% were obtained. All PEN/GN‐nitrile nanocomposite films can stand high temperature, up to 480 °C. Hence, novel dielectric PEN/GN‐nitrile nanocomposite films with excellent mechanical and thermal properties can be used as dielectric materials under some critical circumstances such as high wear and temperature. Copyright © 2012 Society of Chemical Industry     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

Comparative study of physico-mechanical performance of PPC mortar incorporated 1D/2D functionalized nanomaterials

The current study investigates the effect of adding graphene oxide (GO) and functionalized multiwalled carbon nanotubes (FMWCNTs) in pozzolana Portland cement (PPC) mortars to evaluate their mechanical and electrical resistivity properties. The effects of 1D and 2D functionalized carbon nanomaterials in PPC have been studied. At 90 days of curing, the g1PPC (.0015% of GO by weight percentage of binder) and c1PPC (.0015% of FMWCNTs by weight percentage of binder) showed a significant improvement in the physico-mechanical performance of the pozzolana Portland cement composited (PPCC) mortars. The enhanced compressive strength was found to be 11.67% and 8.74% for g1PPC and c1PPC, respectively, as compared to the control specimen (PPC-C). The increased tensile splitting strength was observed to be 26.39% and 20.61% for g1PPC and c1PPC, respectively, as compared to PPC-C. The electrical resistivity of PPCC mortars have been shown a significant improvement for g1PPC and c1PPC. This might be due to the densification of calcium silicate hydrate (C–S–H) gel and hydration products. Powdered X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR). Field emission-scanning electron microscope (FE-SEM) was able to support the improved strength of PPCC mortars via formation of ettringite and needle-shaped crystals in hydrated products.     

Characterization and performance of dodecyl amine functionalized graphene oxide and dodecyl amine functionalized graphene/high‐density polyethylene nanocomposites: A comparative study

Dodecyl amine (DA) functionalized graphene oxide(DA‐GO) and dodecyl amine functionalized reduced graphene oxide (DA‐RGO) were produced by using amidation reaction and chemical reduction, then two kinds of well dispersed DA‐GO/high‐density polyethylene (HDPE) and DA‐RGO/HDPE nanocomposites were prepared by solution mixing method and hot‐pressing process. Thermogravimetric, X‐ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffractions, and Raman spectroscopy analyses showed that DA was successfully grafted onto the graphene oxide surface by uncleophilic substitution and the amidation reaction, which increased the intragallery spacing of graphite oxide, resulting in the uniform dispersion of DA‐GO and DA‐RGO in the nonpolar xylene solvent. Morphological analysis of nanocomposites showed that both DA‐GO and DA‐RGO were homogeneously dispersed in HDPE matrix and formed strong interfacial interaction. Although the crystallinity, dynamic mechanical, gas barrier, and thermal stability properties of HDPE were significantly improved by addition of small amount of DA‐GO or DA‐RGO, the performance comparison of DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites indicated that the reduction of DA‐GO was not necessary because the interfacial adhesion and aspect ratio of graphene sheets had hardly changed after reduction, which resulting in almost the same properties between DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39803.     

聚合物功能化石墨烯的合成及应用研究进展(二)

着重评述了采用共价连接和非共价连接技术制备聚合物功能化石墨烯的方法,介绍了聚合物功能化石墨烯的应用概况。     

聚合物功能化石墨烯的合成及应用研究进展(一)

着重评述了采用共价连接和非共价连接技术制备聚合物功能化石墨烯的方法,介绍了聚合物功能化石墨烯的应用概况。     

Vertically oriented polyaniline‐graphene nanocomposite based on functionalized graphene for supercapacitor electrode

Polyaniline functionalized reduced graphene oxide (PORGO) is prepared by interfacial polymerization and then vertically oriented polyaniline‐graphene (PANI‐PORGO) nanocomposites based on PORGO are developed successfully by in situ polymerization. The morphology and structure are characterized by field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT‐IR), Raman spectra and X‐ray diffraction (XRD). The electrochemical tests indicate that the specific capacitance of PORGO and PANI‐PORGO is as high as 291 and 369 F/g, respectively, at the current density of 1 A/g. PANI—PORGO nanocomposite exhibits high electrochemical activity and enhanced cycle stability with a capacitance retention of 81.2% after 500 cycles at 10 A/g. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44808.     

Adsorption of Hg(Ⅱ) from aqueous solution using thiourea functionalized chelating fiber

A fast and selective adsorbent for Hg(II) from aqueous solutions using thiourea(TU) functionalized polypropylene fiber grafted acrylic acid(PP-g-AA),PP-g-AA-TU fibers,was characterized by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.The adsorption behavior of the functionalized chelating fibers for Hg(II) was investigated by static adsorption experiments,and the effects of some essential factors on adsorption of Hg(II) were examined,such as pH,initial concentration,adsorption time,coexisting cations,and temperature.The results showed that the adsorptive equilibrium could be achieved in 10 min,and the equilibrium adsorption quantity of PP-g-AA-TU fibers was 20 times that of PP-g-AA fibers.The PP-g-AA-TU fibers showed a very high adsorption rate and a good selectivity for Hg(II) over a wide range of p H.The adsorption isotherm can be well described with Langmuir model,with the maximum adsorption capacity for Hg(II) up to52.04 mg·g~(-1)and the removal of Hg(II) more than 97%.The kinetic data indicate that the adsorption process is best-fitted into the pseudo-second-order model.     

染料共价改性石墨烯及其水分散性研究

本文以石墨粉为原料，以直接灰D为改性剂，将其重氮化后共价接枝到自制的还原氧化石墨烯（rGO）上，制备改性石墨烯（MG），以提高石墨烯在水中的分散性，使其更适用于纺织品整理。采用拉曼光谱（Raman）、傅立叶红外光谱（FTIR）、高分辨X射线光电子能谱（XPS）、热重分析（TGA）等表征手段对得到的改性石墨烯进行表征。结果表明，染料分子成功接枝到石墨烯上，接枝率达到21%左右。采用紫外-可见分光光度计（UV-vis）考察了改性石墨烯在水中的分散性。结果发现，相对rGO，MG在水中的分散性和稳定性都大大提高，其水溶液的最大饱和度达到0.185 mg/mL，静置7天后，仍可达到0.092 mg/mL。改性后的石墨烯同时具备了染料和石墨烯的性能。     

功能化石墨烯改性双马来酰亚胺复合材料的微观表征及性能

采用改进Hummers法制备氧化石墨烯（GO）,分别采用水合肼、壳聚糖、KOH还原得到了还原氧化石墨烯（rGO）并对三种还原方法做了对比,选择最佳方案;再通过离子液体（NH₂IL）对rGO功能化得到改性还原氧化石墨烯（NH₂IL-rGO）。以二烯丙基双酚A （BBA）和双酚A双烯丙基醚（BBE）为活性稀释剂,4,4'-二氨基二苯甲烷型双马来酰亚胺（MBMI）为反应单体,制备了MBMI-BBA-BBE （MBAE）树脂基体;同时以NH₂IL-rGO为增强体采用原位聚合法制备NH₂IL-rGO/MBAE复合材料。表征了石墨烯和复合材料的微观形貌并分析了石墨烯对复合材料性能的影响。结果表明：NH₂IL-rGO在树脂基体中以两相形式存在,结构完整,并赋予复合材料优异的性能。当NH₂IL-rGO含量为2%（质量）时,复合材料冲击强度和弯曲强度最大,分别为15.33 kJ/m²和142 MPa,热分解温度为435.73℃、当测试频率为100 Hz～10 kHz时介电常数发生突变达到84。     

UV固化TiO_2光催化涂料的制备及性能研究

以六亚甲基二异氰酸酯(HDI)三聚体、二乙醇胺、甲基丙烯酸缩水甘油酯(GMA)为主要原料合成了低分子量多官能度UV固化预聚物。以该预聚物为成膜树脂,与锐钛型Ti O2乙醇分散液混合,制备了UV固化Ti O2光催化涂层。采用傅里叶变换红外光谱、1H–核磁共振、凝胶色谱等对合成预聚物的结构和性能进行表征。探讨了Ti O2含量对涂层附着力、铅笔硬度、耐水性、水接触角和光照稳定性的影响,研究了在模拟太阳光照下不同Ti O2含量UV固化涂层对水中亚甲基蓝的光催化降解作用。结果表明,Ti O2含量为0.9%时,涂层具有较好的机械性能和耐水性,且2 h就可使亚甲基蓝溶液褪色。通过热重分析仪测得涂层的起始分解温度为220°C,热稳定性较好。     

Improved H2-generation performance of Pt/CdS photocatalyst by a dual-function TiO2 mediator for effective electron transfer and hole blocking

Surface modification with noble metal cocatalysts was proved to be a useful route for boosting photocatalytic efficiency of various photocatalysts. Nevertheless, considering the random dispersion of metallic cocatalysts on the photocatalyst surface, the noble metal-loaded photocatalyst generally shows a limited enhancement of its activity because the noble metals can also work as the recombination sites of photoinduced charges. In this paper, TiO₂ as a dual-function mediator (for effective electron transport and hole block) is successfully introduced into the interface of Pt and CdS to form PtTiO₂/CdS photocatalyst, with an aim of suppressing the high recombination rate of electron-hole pairs on the Pt active sites. Under visible light, all the prepared PtTiO₂/CdS displayed distinctly enhanced photocatalytic hydrogen-generation performance and the PtTiO₂/CdS(8%) attains the highest photocatalytic H₂-production rate (294.2?μmol/h), a value significantly higher than that of Pt/CdS about 3.2 time. A dual-function TiO₂-mediated mechanism was put forward to account for the superior hydrogen production of PtTiO₂/CdS photocatalyst, namely, the TiO₂ layer in the PtTiO₂/CdS not only works as electron-transport layers to effectively transfer photogenerated electrons to promote the H₂-production reaction on Pt cocatalysts, but also acts as hole-block layer to prevent the possible recombination of photogenerated charges on the Pt active sites, resulting in a distinct improvement of final H₂-generation activity.     

TiO2改性石墨烯电极电吸附去除污水中NH4+

通过水热法制备得到TiO₂改性石墨烯复合材料（RGO/TiO₂）,考察了其形貌结构和电化学性能。将其组装成电极,对比未改性石墨烯（RGO）电极和RGO/TiO₂电极的电吸附NH₄⁺性能。重点考察外加电压、循环流速、初始浓度等工艺参数对RGO/TiO₂电极电吸附NH₄⁺的影响,并对其电吸附NH₄⁺特性和对模拟实际含NH₄⁺废水深度脱NH₄⁺效果进行研究。结果表明：RGO/TiO₂复合材料具有三维孔洞结构,比表面积为382.08 m²·g^-1,比电容量在扫速为0.01 V·s^-1时达到325.80 F·g^-1,优于RGO材料。RGO/TiO₂电极的初次电吸附量较RGO电极提升了28.3%,循环再生吸附10次后,RGO/TiO₂电极的NH₄⁺吸附量仅降低了5.87%,循环再生吸附性能优于RGO电极。外加电压2.0 V、循环流速35 ml·min^-1和NH₄⁺初始浓度1.0 mmol·L^-1为RGO/TiO₂电极的最佳NH₄⁺电吸附条件。RGO和RGO/TiO₂电极电吸附NH₄⁺过程符合准一级动力学模型和Freundlich等温吸附模型,电吸附NH₄⁺为非均匀表面的多层吸附行为,以物理吸附为主。RGO/TiO₂电极4级串联时对模拟实际含NH₄⁺炼油净化水的去除率达到86.84%。     

Designed nitrogen doping of few-layer graphene functionalized by selective oxygenic groups

Few-layer nitrogen doped graphene was synthesized originating from graphene oxide functionalized by selective oxygenic functional groups (hydroxyl, carbonyl, carboxyl etc.) under hydrothermal conditions, respectively. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) observation evidenced few-layer feature of the graphene oxide. X-ray diffraction (XRD) pattern confirmed phase structure of the graphene oxide and reduced graphene oxide. Nitrogen doping content and bonding configuration of the graphene was determined by X-ray photoelectron spectroscopy (XPS), which indicated that different oxygenic functional groups were evidently different in affecting the nitrogen doping process. Compared with other oxygenic groups, carboxyl group played a crucial role in the initial stage of nitrogen doping while hydroxyls exhibited more evident contribution to the doping process in the late stage of the reaction. Formation of graphitic-like nitrogen species was controlled by a synergistic effect of the involved oxygenic groups (e.g., -COOH, -OH, C-O-C, etc.). The doping mechanism of nitrogen in the graphene was scrutinized. The research in this work may not only contribute to the fundamental understandings of nitrogen doping within graphene but promote the development of producing novel graphene-based devices with designed surface functionalization.     

Removal of ammonium ions in wastewater by electrosorption with TiO2 modified graphene electrode

In this study, the TiO₂ modified graphene composite material (RGO/ TiO₂) was prepared by hydrothermal method, and its morphological structure and electrochemical properties were investigated. Then RGO/TiO₂ material was assembled into electrode, and NH₄⁺ ions electrosorption efficiencies of unmodified graphene (RGO) electrode and the RGO/TiO₂ electrode were compared. The effects of applied voltage, circulating velocity and initial concentration on NH₄⁺ ions electrosorption by RGO/TiO₂ electrode were investigated. The characteristics of NH₄⁺ ions electrosorption and the effect of advanced NH₄⁺ ions removal from simulated actual wastewater containing NH₄⁺ ions were also studied. The results showed that the RGO/TiO₂ composite material had a three-dimensional pore structure with specific surface area of 382.08 m²·g^-1 and specific capacitance of 325.80 F·g^-1 at a scan rate of 0.01 V·s^-1, which were better than those of the RGO material. The initial adsorption capacity of RGO/TiO₂ electrode was 28.3% higher than that of RGO electrode. After 10 cycles of regeneration adsorption, the adsorption capacity of NH₄⁺ ions of RGO/TiO₂ electrode only decreased 5.87%, and its cyclic regeneration adsorption property was better than that of RGO electrode. In addition, the applied voltage 2.0 V, circulating velocity 35 ml·min^-1 and initial concentration 1.0 mmol·L^-1 were the optimal NH₄⁺ ions electrosorption conditions for RGO/TiO₂ electrode. The electrosorption process of NH₄⁺ ions by RGO and RGO/TiO₂ electrodes was in accordance with the quasi-first-order kinetic model and the Freundlich isothermal adsorption model. The electrosorption of NH₄⁺ ions was a multi-layer adsorption behavior on heterogeneous surface and physical adsorption was the dominant. When the RGO/TiO₂ electrode was connected in 4-stage series, the removal efficiency of simulated actual NH₄⁺ refining purified water reached 86.84%.     

多孔胺基化氧化石墨烯基材料对CO2的吸附性能研究

以乙二胺(EDA)、二乙烯三胺(DETA)、四乙烯五胺(TEPA)、聚乙烯亚胺(PEI)等多胺基化合物为表面改性剂,氧化石墨烯(GO)材料为载体,采用嫁接法辅以超声处理制备了表面胺基功能化多孔吸附材料,用于CO₂气体的吸附捕集。所制备的多孔吸附材料孔径约为1.35~4.34 nm,比表面积约为98.032~210.465 m²/g。制备的四种吸附材料中,以PEI功能化吸附材料对CO₂的吸附容量最大,70℃下达到了1.5 mmol/g,且经过20次循环吸附/脱附实验后,其CO₂吸附量基本不变。吸附过程的吸附等温线线型为Ⅰ型优惠型,另外吸附实验数据与Avrami模型模拟结果符合性较好。