Synthesis,mechanical, and barrier properties of LDPE/graphene nanocomposites using vinyl triethoxysilane as a coupling agent

Precise interface control and dispersal of graphene nanosheets in polymer hosts are challenging to develop high performance graphene-based nanocomposites due to their strong interlayer cohesive energy and surface inertia. Here, we firstly report an efficient and novel method to functionalize graphene nanosheets with vinyl triethoxysilane (VTES) and successfully blend them with low density polyethylene (LDPE) to prepare nanocomposites. Fourier transforms infrared spectra (FTIR), Raman spectra, and thermogravimetric analysis (TGA) proved that the graphene sheets were covalently bonded with VTES. The resulting nanocomposites obtained the increases of up to 27.0 and 92.8% in the tensile strength and Young’s modulus, respectively, compared to neat LDPE. The VTES–graphene not only remarkably improved the tensile strength of the composites, but also enhanced its toughness by 17.7%. Oil permeability measurements showed that the absorption ratio of toluene by the LDPE/graphene composites decreased from 56 to 39%, and its barrier properties have obviously been improved. This study opens a new route to optimize interface structures and improve the comprehensive performances of graphene–polymer nanocomposites.     

Modified π-states in ion-irradiated carbon

CVD polycrystalline diamond film, pulse laser-deposited (PLD) carbon film and highly oriented pirolitical graphite (HOPG) as reference, were modified by means of Ar⁺ ion bombardment and characterized by means of Raman scattering, transmission electron microscopy, electron-diffraction (TEM), reflected electron energy loss specroscopy (REELS) and X-ray photoelectron spectroscopy (XPS) techniques. It was found that the diamond was transferred to a carbon with halo-like morphology and disordered stack of graphene segments. Instead of the well-known electron energy loss peak of graphite at 6.5 eV, a new REELS peak appeared at 4-5 eV energies. The observed effect was explained by the modification of π-system in carbon films as a consequence of the formation of non-planar, nanometer-sized graphitic planes.     

Kinetics of Isothermal and Nonisothermal Crystallization of Poly(ethylene oxide) (PEO) in PEO/Fatty Acid Blends

In this work, isothermal and nonisothermal crystallization kinetics of poly(ethylene oxide) (PEO) and PEO in PEO/fatty acid (lauric and stearic acid) blends, that are used as thermal energy storage materials, was studied using differential scanning calorimetry (DSC) data. The Avrami equation was adopted to describe isothermal crystallization of PEO and nonisothermal crystallization was analyzed using both the modified Avrami approach and Ozawa method. Avrami exponent (n) for PEO crystallization was in the range 1.08–1.32 (10–90% relative crystallinity), despite of spherulites formation, while for PEO in PEO/fatty acid blends n was between 1.61 and 2.13. Hoffman and Lauritzen theory was applied to calculate the activation energy of nucleation (K_g) – the lowest value of K_g was observed for pure PEO, despite of heterogeneous nucleation of fatty acid crystals in PEO/fatty acid blends. For nonisothermal crystallization of PEO in PEO/lauric acid (1:1 w/w) and PEO/stearic acid (1:3 w/w) blends, secondary crystallization occurred and values of the Avrami exponent were 2.8 and 2.0, respectively. The crystallization activation energies of PEO were determined to be ?260 kJ/mol for pure PEO, ?538 kJ/mol for PEO/lauric acid blend, and ?387 kJ/mol for PEO/stearic acid blend for isothermal crystallization and ?135,6 kJ/mol, ?114,5 kJ/mol, and ?92,8 kJ/mol, respectively, for nonisothermal crystallization.     

Curcumin-assisted ultrasound exfoliation of graphite to graphene in ethanol

In this paper, we demonstrated a simple and cost-effective method to produce graphene from graphite in ethanol using ultrasound assisted with curcumin. The influence of curcumin concentration, starting graphite amount, sonication power, and sonication time on the graphene concentration was studied schematically. The π-π interaction between curcumin and graphene, being confirmed by FTIR spectrum, facilitate the exfoliation of the graphite into graphene. The concentration of the graphene in the ethanol reached up to 1.44 mg mL⁻¹ and the exfoliated suspension was relatively stable. The content of monolayer, bilayer, and multilayer in the exfoliated graphene suspension were 21%, 37%, and 42%, respectively. The as-prepared graphene sheets were free-defect. This novel approach may not only enable to exfoliate the graphite into graphene but also to make the graphene-curcumin hybrid which might find applications in pharmaceutical industry.     

Enhanced photocatalytic activity of graphene–TiO2 composite under visible light irradiation

Novel graphene–TiO₂ (GR–TiO₂) composite photocatalysts were synthesized by hydrothermal method. During the hydrothermal process, both the reduction of graphene oxide and loading of TiO₂ nanoparticles on graphene were achieved. The structure, surface morphology, chemical composition and optical properties of composites were studied using XRD, TEM, XPS, DRS and PL spectroscopy. The absorption edge of TiO₂ shifted to visible-light region with increasing amount of graphene in the composite samples. The photocatalytic degradation of methyl orange (MO) was carried out using graphene–TiO₂ composite catalysts in order to study the photocatalytic efficiency. The results showed that GR–TiO₂ composites can efficiently photodegrade MO, showing an enhanced photocatalytic activity over pure TiO₂ under visible-light irradiation. The enhanced photocatalytic activity of the composite catalysts might be attributed to great adsorptivity of dyes, extended light absorption range and efficient charge separation due to giant π-conjugation system and two-dimensional planar structure of graphene.     

Surface treatment of magnesium hydroxide to improve its dispersion in organic phase by the ultrasonic technique

Micron magnesium hydroxide [Mg(OH)₂] was modified by means of ultrasonic method with stearic acid (SA) as modifier in water. The Fourier transform infrared spectroscopy (FT-IR) and element analysis showed all SA was bonded upon the surface of the Mg(OH)₂ forming a coating layer and no free SA was detected after the modifying process. The thickness of coating SA on the Mg(OH)₂ was determined by X-ray photoelectron spectroscopy (XPS). Compared with the unmodified Mg(OH)₂, the modified Mg(OH)₂ had better dispersion property in xylene, slower sedimentation velocity of dilute suspension in xylene and lower viscosity of suspension in paraffin liquid. The results showed that the modified Mg(OH)₂ could be dispersed much better than the unmodified Mg(OH)₂ in organic phase.     

A frequency response study of thiophene adsorption in zeolite catalysts

The frequency response (FR) technique has been applied to study adsorption processes of thiophene (TP) on NaY zeolite and CeY zeolite. The FR spectra of TP on NaY and CeY were recorded at temperatures between 335 and 473 K and in the pressure range of 0.1-4.0 Torr. On NaY and CeY, adsorption of thiophene (TP) in the supercage is found to be the rate-controlling step and diffusion of benzene in the supercage is the rate-controlling step, respectively. On NaY, the adsorption process by π-electronic interaction of TP and adsorption via pore-filling mechanism were caught. Adsorption by π-electronic interaction is not the main sorption process but its effect is significant. While on Ce³⁺Y, the adsorption processes relating to the π-complexation and the direct forming of SM bond were observed, the adsorption by forming π-complexation is the main process. The relaxation time of the strong sorption interaction coming from the FR spectrum is two orders magnitude shorter than that of the weak adsorption process and the number of sites available for adsorption of TP in each process is calculated. The value of relaxation time reflects the ability of different processes and concentration of adsorption site. Combining the FR spectra and other methods such as isotherms and Langmuir model, thoroughly understanding of the thiophene adsorption process in zeolites can be got.     

Signatures of different carbon bonds in graphene oxide from soft x‐ray reflectometry

In graphene oxide, the graphite lattice is intercalated with oxygen groups that bond to carbon atoms. These groups have a bearing on the possibility of using graphene oxide as a precursor to make graphene. The nature of carbon bonds in graphene oxide has been characterized with soft x‐ray reflection spectroscopy across the carbon K‐edge. Results distinguish graphene oxide synthesized with Hummers' method from that made using a method suggested by Tour. The observed spectra are consistent with those from near‐edge x‐ray absorption fine structure (NEXAFS) measurements. In particular, the expected carbon K‐edge resonances associated with excitations into molecular π*‐ and σ*‐states of C? C bonds can be identified. Importantly, the greater oxidation efficiency of the method by Tour may be the reason for the observation of additional resonances that have been assigned to carbon bonding with molecular groups containing oxygen. The additional resonances have been interpreted as the excitations of carbon 1 s electrons into the carbonyl π*(C?O) orbital in the molecular group –COOH and into the hydroxyl π*(C? OH) orbital, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and microstructure of metal oxide thin films containing metal nanoparticles by liquid phase deposition (LPD) method

Au nanoparticles dispersed SiO₂-TiO₂ composite films have been prepared by a novel wet process, Liquid Phase Deposition (LPD) method. The composite films were characterized by XRD, XPS, TEM, ICP, SEM and UV-VIS absorption spectroscopy. The results showed that the SiO₂-TiO₂ composite films containing Au^III and Au^I ionic species were co-deposited from a mixed solution of ammonium silicofluoride, ammonium hexafluorotitanate, boric acid and tetrachloroauric acid. The heat treatment induced the reduction of Au ions and formation of Au nanoparticles in the film. TEM observation revealed that the Au nanoparticles with 5-10 nm in diameter were found to be dispersed uniformly in the SiO₂-TiO₂ matrix. The optical absorption band due to the surface plasmon resonance of dispersed Au particles were observed at the wavelength of 550 nm and shifted toward longer wavelength with increasing heat treatment temperature. Received 28 November 2000     

Synthesis and characterization of water-soluble carbon nanotubes from mustard soot

Carbon nanotubes (CNT) has been synthesized by pyrolysing mustard oil using an oil lamp. It was made water-soluble (wsCNT) through oxidative treatment by dilute nitric acid and was characterized by SEM, AFM, XRD, Raman and FTIR spectroscopy. The synthesized wsCNT showed the presence of several junctions and defects in it. The presence of curved graphene structure (sp²) with frequent sp³ hybridized carbon is found to be responsible for the observed defects. These defects along with the presence of di- and tri-podal junctions showed interesting magnetic properties of carbon radicals formed by spin frustration. This trapped carbon radical showed ESR signal in aqueous solution and was very stable even under drastic treatment by strong oxidizing or reducing agents. Oxidative acid treatment of CNT introduced several carboxylic acid group functionalities in wsCNT along with the nicking of the CNT at different lengths with varied molecular weight. To evaluate molecular weights of these wsCNTs, an innovative method like gel electrophoresis using high molecular weight DNA as marker was introduced.     

Simple method for synthesizing few-layer graphene as cathodes in surface-enabled lithium ion-exchanging cells

In order to realize a wider application for graphene materials specifically in the field of energy storage, a simple and mass-scalable method described as “the atmospheric, low-temperature, shock-heating process” is proposed in this work. During this low-temperature process, the graphite oxide without pre-treatment is completely exfoliated to form the few-layer graphene materials at atmospheric conditions. The Brunauer-Emmett-Teller (BET)-specific surface area of acquired material at 350 °C can reach 487 m² g^?1. The acquired few-layer graphene materials are also confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM). The results demonstrate that this simple method is feasible for synthesizing the few-layer graphene materials. Besides that, the acquired graphene is also used as the cathode material in the surface-enabled lithium ion-exchanging cell. The galvanostatic charge/discharge tests show that the graphene prepared from this method is suitable for this system and displays a satisfactory electrochemical performance. The acquired graphene sample exhibits the reversible capacities of around 187, 107, 84, 58, and 45 mAh g^?1 at 0.1, 2, 5, 10, and 15 A g^?1, respectively. At the current density of 0.5 A g^?1, the capacity retention can reach 75 % after 2000 cycles.     

Hollow polypyrrole nanosphere embedded in nitrogen-doped graphene layers to obtain a three-dimensional nanostructure as electrode material for electrochemical supercapacitor

A novel approach was developed to prepare hollow polypyrrole (PPy) nanospheres and nitrogen-doped graphene/hollow PPy nanospheres (NG/H-PPy) composites. In this process, uniform poly (methyl methacrylate-butyl methacrylate-methacrylic acid) (PMMA-PBMA-PMAA) latex microspheres as sacrificial templates were synthesized by using an emulsion polymerization method. Then, hollow PPy nanospheres were obtained on the surface of PMMA-PBMA-PMAA microspheres by in situ chemical oxidative polymerization. Finally, H-PPy was embedded in NG layers successfully through a simple approach. The nanobeads have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectra, and Fourier transform infrared spectra (FTIR). Different electrochemical methods including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) have been applied to study the electrochemical properties. The specific capacitance of NG/H-PPy composites based on the three-electrode system is as high as 575 F g^?1 at a current density of 1 A g^?1 and enhanced stability about 90.1 % after 500 cycles, indicating that the composite has an impressive capacitance and excellent cycling performance.     

Modification of Low Density Polyethylene with 2-Hydroxyethyl Acrylate by a Swollen-Phase Grafting Method

Low-density polyethylene (LDPE) was modified with 2-hydroxyethyl acrylate (HEA) by a swollen phase grafting method with azobisiso-butyronitrile (AIBN) as initiator and xylene as a swelling agent. Fourier transform infrared spectroscopy (FTIR) and ¹H-nuclear magnetic resonance (¹H-NMR) showed that the HEA was grafted onto the PE molecular chains and the copolymer (LDPE-g-PHEA) was formed. The rheological data illustrated that the content of long chain branches (LCB) in LDPE-g-PHEA was higher than in LDPE. Melt flow index (MFI) measurements indicated that the LDPE backbone was degraded slightly when the HEA content was small in the process of grafting. X-ray diffraction (XRD) and water contact angle measurements demo-nstrated that the grafting degree had an influence on the crystallinity and polarity of the graft polymer. A staining analysis indicated that the dyeing of the product was improved continuously with increasing of the grafting degree. Polyvinylpyrrolidone (PVP), NaCl, and ultrasound were shown to contribute to the staining, with ultrasound being the most productive. The probable grafting reaction mechanism is pro-posed. The results of the influence of monomer concentration on the grafting reaction revealed that the grafting ratio and gel content of the product increased with increasing of HEA amount.     

Crystallization Behavior of Poly(Lactic Acid) Filled with Modified Carbon Black

A novel method was employed to modify the surface of carbon black (CB) by an organic small molecule in a Haake Rheomix mixer. The modified carbon black (MCB) was dispersed uniformly in poly(lactic acid; PLA). The crystallization behaviors of PLA, PLA/CB and PLA/MCB composites were investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) and polarizing optical microscopy. It is found that the addition of CB or MCB can influence the crystallization behavior of PLA. PLA/MCB has a faster crystallization rate and higher crystallization peak temperature than PLA/CB. For non-isothermal studies, Jeziorny and Mo equations were employed. The Mo equation can well describe the non-isothermal crystallization of the three samples. For PLA/CB and PLA/MCB composites containing 3wt% fillers, the nucleating activity for CB is about 0.32, and about 0.16 for MCB. All these results show that MCB is an effective nucleating agent. PLA/MCB has a higher nucleation rate than PLA/CB because of the finer dispersed particles size and improved interaction between MCB and PLA.     

Investigation of Raman and photoluminescence studies of reduced graphene oxide sheets

In this paper, we are investigating the Raman and photoluminescence properties of reduced graphene oxide sheets (rGO). Moreover, graphene oxide (GO) sheets are synthesized using Hummer’s method and further reduced into graphene sheets using D-galactose. Both GO and rGO are characterized by UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Thermogravimetric (TGA) analysis. Raman analysis of rGO shows the restoration of graphitic domains in GO after reduction. The photoluminescence of rGO showed emission in the UV region which is blue shifted along with luminescent quenching as compared to GO. This blue shift and quenching in photoluminescence arises due to the newly formed crystalline sp² clusters in rGO which created percolation pathways between the sp² clusters already present.     

Non-isothermal crystallization kinetics of alkyl-functionalized graphene oxide/high-density polyethylene nanocomposites

Dodecyl amine-functionalized graphene oxide (DA-GO) was obtained via an amidation reaction. The results of X-ray diffraction and Fourier-transform infrared spectroscopy verified that long alkyl chains of DA were successfully grafted on the GO sheets. Transmission electron microscope and scanning electron microscope techniques illustrated that homogeneously dispersed DA-GO/high-density polyethylene (HDPE) nanocomposites were obtained. The effects of DA-GO on the non-isothermal crystallization of HDPE were then investigated by differential scanning calorimetry (DSC) at various cooling rates (2, 5, 10, and 20?°C/min). Significant increase in the onset crystalline temperature (T_o) and the peak crystallization temperature (T_p) of HDPE incorporating DA-GO indicated the strong nucleating ability of DA-GO. The investigation of half-time crystallization time (t_1/2) demonstrated that crystallization rate of HDPE consisting of DA-GO is faster than that of pure HDPE at a given cooling rate. Ozawa, Avrami, and the combined Avrami–Ozawa methods (Mo) were used for analyzing experimental data. The Mo approach was successful in describing the non-isothermal crystallization process of DA-GO/HDPE nanocomposites. The results indicated that low DA-GO content accelerates the crystallization of HDPE, while higher content hinders the crystallization of HDPE.     

Chemical modification of the surface of Fe<Subscript>75</Subscript>Si<Subscript>25</Subscript> alloy particles with stearic acid under high-energy ball-milling conditions

The morphology, phase composition and surface structure of Fe₇₅Si₂₅-alloy particles are studied by electron microscopy, X-ray diffraction analysis, and Mössbauer, Auger, IR (infrared) and X-ray photoelectron spectroscopy. The alloy particles used as fillers for the polyethylene matrix are produced by high-energy ball milling in an organic medium with the addition of stearic acid. The addition of stearic acid is shown to promote plasticization of the brittle Fe₇₅Si₂₅ alloy and the formation of a surface layer of no more than 1.5 nm thick, consisting of oxides based on iron and silicon, responsible for the chemisorption of stearic acid on the surface. Chemical modification of the surface of filler particles with an amphiphilic surfactant is carried out to enhance their adhesion in the polymer matrix.     

RTV Silicone Rubber Filled with Surface Modified Montmorillonite

The surface modification of pristine montmorillonite (MMT) with four kinds of coupling agents for reinforcement of the room temperature vulcanized vinyl-terminated polydimethylsiloxane (RTV PDMS) networks was investigated. The four coupling agents containing γ-glycidoxypropyltrimethoxysilane (KH-560), γ-methacryloxypropyltri methoxysilane (KH-570), isopropyl trioleic titanate (NDZ-105), and stearic acid (SA) without N, P, or S compounds were used because the coupling agents harmless to the platinum catalyst used normally in the curing of RTV vinyl-terminated PDMS. The interaction between MMT particles and coupling agents was confirmed by diffused reflectance infrared spectroscopy (DR-FTIR) tests. By scanning electron microscopy (SEM) characterization, surface modified MMT was dispersed heterogeneously in the PDMS matrix for all four coupling agents. By X-ray diffraction (XRD) characterization, the interlayer distances of the four surface modified MMT were not changed. Dielectric tests showed that the dielectric constant and dielectric loss of PDMS filled with KH-560, KH-570, and SA treated MMT were decreased comparing with those of PDMS filled with pristine MMT. With the increasing content of MMT treated with KH-570, the dielectric constant and dielectric loss value of PDMS composites increased.     

纳米孔模板浸润法制备聚乙烯纳米线阵列的热导率的实验研究

采用纳米孔模板润湿技术制备了直径为200 nm的低密度聚乙烯(LDPE)纳米线阵列, 并利用纳秒激光闪光法测量了20—80℃时LDPE纳米线阵列的热导率. 测量得到室温时LDPE纳米线阵列的热导率为2.2 W/mK, 大约比其体材料的热导率高1个数量级, 并且纳米线阵列的热导率随温度的升高略有增加. 忽略纳米线之间的声子散射, 估算得到室温下单根LDPE纳米线的热导率高于5 W/mK. 本文制备LDPE纳米线热导率的提高源自其分子链定向度增加导致的低维导热效应的增强, 纳米线的分子链定向度受工艺过程中流体剪切、振动、分子链迁移运动、 纳米孔约束等几种因素的综合影响.     

氧化石墨烯增强Cu-Nb 复合线材结构及性能影响研究

本文采用粉末套管法成功制备出氧化石墨烯增强的 GO/Cu-Nb 多芯(192 芯) 复合线材及未掺杂氧化石墨烯的 Cu-Nb 多芯(192 芯) 复合线材. 通过金相、SEM 及拉曼光谱等表征不同尺寸下两种复合线材的芯丝组态、 界面特征及特征峰. 结果表明, 氧化石墨烯由于良好的自润滑特性较好地协调了芯丝与基体的变形, 其弥散分布有效阻隔了 Nb 颗粒团聚及大尺寸晶粒的产生, 芯丝变形更均匀, 形态更规则. 力学和电学性能测试结果表明, 掺杂氧化石墨烯后,Cu-Nb 复合线材的力学与电学性能均明显提升, 分析认为, 氧化石墨烯的尺寸大小、 分散均匀性及热处理是影响线材综合性能提升的主要原因.