CF<Subscript>4</Subscript> plasma-induced grafting of fluoropolymer onto multi-walled carbon nanotube powder

Grafting of fluoropolymer onto multi-walled carbon nanotube (MWCNTs) powder by CF₄ plasma treatment was investigated in this study. In order to achieve a uniform treatment of powder, a rotating barrel was designed and fixed between the two discharge electrodes. The influence of various plasma parameters, such as power and treatment time, on the fluorination of MWCNT surface was systematically analyzed by X-ray photoelectron spectroscopy (XPS), Fourier transformed infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results revealed that a successful fluorination of MWCNT powder with a maximum of fluorine content of 12% could be achieved by using our plasma equipment. Our work provides a new way for the homogeneous fluorination of MWCNT powder and is valuable for industrial production. PACS 52.50.Dg; 52.40.Mj; 52.59. Ye; 52.77.-j     

Effect of doping functionalized MWCNTs on the electrochemical performances of Li<Subscript>2</Subscript>CoSiO<Subscript>4</Subscript> for lithium-ion batteries

We report the synthesis of Li₂CoSiO₄ by the sol-gel method and the preparation of a composite electrode by incorporating functionalized multi-walled carbon nanotubes (fn. MWCNTs) as conductive additive. XRD pattern of the composite confirms the structural stability of Li₂CoSiO₄ even after the addition of fn. MWCNTs. SEM images of the composite reveal the presence of conductive bridges formed by MWCNTs between the submicron-sized particles of Li₂CoSiO₄. The cyclic voltammograms of the composite cathode show redox peaks with higher current density than pure Li₂CoSiO₄ and the current density increases with increase in sweep rate. The diffusion coefficient of lithium has been improved by the addition of fn. MWCNTs from 1 × 10^?14 to 8 × 10^?14 cm²/s as calculated using Randles-Sevcik equation. The charge-discharge cycling performance of both pure Li₂CoSiO₄ and composite cathode has been discussed.     

Formation of well-packed TiO<Subscript>2</Subscript> nanoparticles on multiwall carbon nanotubes using CVD method to fabricate high sensitive gas sensors

Titanium oxide nanoparticles were coated on multiwall carbon nanotubes (MWCNTs) using an atmospheric pressure chemical vapor deposition (CVD) to achieve highly compact nanoparticles of about 5 nm on CNT structure. The CNTs with a diameter of about 50 nm were grown by plasma enhanced CVD. Gas sensitivity of the fabricated structure was investigated and compared with TiO₂/CNT composite-based gas sensors. The effect of the structural interaction between the nanoparticles and the CNT wall on sensing mechanism of the as-prepared gas sensors was investigated. Ultrasensitive gas sensors were obtained by TiO₂/CNT nanostructures with strong interaction between the MWCNT and the TiO₂ nanoparticles. The measurements show high chemical activity and exceptional electrical response of the as-prepared structure being exposed to gases. Scanning and transmission electron microscopy and X-ray diffraction analysis were used to obtain structural information.     

Electrical and optical characterization of pulsed plasma of N<Subscript>2</Subscript>–H<Subscript>2</Subscript>

This paper considers the electrical and optical characterization of glow discharge pulsed plasma in N₂/H₂ gas mixtures at a pressures range between 0.5 and 4.0 Torr and discharge current between 0.2 and 0.6 A. Electron temperature and ion density measurements were performed employing a double Langmuir probe. They were found to increase rapidly as the H₂ percentage in the mixture was increased up to 20%. This increase slows down as the H₂ percentage in the gas mixture was increased above 20% at the same pressure. Emission spectroscopy was employed to observe emission from the pulsed plasma of a steady-state electric discharge. The discharge mainly emits within the range 280–500 nm. The emission consists of N₂ (C-X) 316, 336, 358 nm narrow peaks and a broad band with a maximum at λ_max = 427 nm. Also lines of N₂, N₂ ⁺ and NH excited states were observed. All lines and bands have their maximum intensity at the discharge current of 0.417 A. The intensities of the main bands and spectral lines are determined as functions of the total pressure and discharge current. Agreement with other theoretical and experimental groups was established.     

Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

Surface modification of multi-walled carbon nanotubes by O2 plasma

The surface modification of multi-walled carbon nanotubes (MWCNTs) by O₂ plasma was carried out in this study. In order to achieve a relatively homogeneous treatment of MWCNTs powder, a rotating barrel fixed between the two discharge electrodes was used. The effect of plasma treatment parameters, such as power, time, and positions of samples (inside and outside the barrel), on the morphology and structure of MWCNTs surface was systematically analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results showed that the direct discharge (outside the barrel) could result in not only a quick grafting of polar functional groups but also an easy damage of MWCNTs after longer time, particularly under intensive power. It was found that the surface of MWCNTs powder might be changed in three steps—expansion (loosed structure formed), peel off and oxidization with increasing of treatment time during the irradiation. In this way, a complete purification of MWCNTs powder could be finished within 30 min via plasma treatment. Our work suggested that plasma treatment could be a simple and nonpolluting method for a large scale purification of MWCNTs.     

Carbon monoxide sensors based on SnO<Subscript>x</Subscript> nanoparticles

Sensors highly sensitive to CO gas that are based on Ag-doped SnO₂ nanoparticles are shown to be a feasibility. The structure and composition of the respective films versus the SnO₂ nanoparticle size are studied. The electrical parameters of the sensor materials are measured. It is shown that exposure of the nanostructured films to carbon monoxide considerably decreases their resistance and shifts the frequency of a maximum in the impedance curves toward lower values. Specific features of the IR reflection spectra in the range of excitation of carbon and oxygen atom vibrations are revealed.     

Effects of dielectric barrier discharge in air on morphological and electrical properties of graphene nanoplatelets and multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) have been functionalized by dielectric barrier discharge (DBD) in air. The extent of functionalization of MWCNTs and GNPs reaches a maximum at the delivered discharge energy of 720 and 240 J mg⁻¹, respectively. Further exposure to plasma leads to reduction of functional groups from the surface of the treated nanomaterials. It has also been demonstrated that DBD plasma does not produce dramatic structural changes in MWCNTs, while flakes of the treated GNPs become thinner and smaller in the lateral size. Conductive thin films, obtained by drop casting a solution of the treated nanomaterials in N-methyl-1-pyrrolidone on poly(methyl methacrylate) substrate, show significantly lower sheet resistance.     

Computer calculations for thermal behavior of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Li<Subscript>2</Subscript>CO<Subscript>3</Subscript> melt

The thermal behavior of Na₂CO₃+Li₂CO₃ melt is studied by the method of thermodynamic simulation. The equilibrium compositions of the gas and salt phases are calculated at different temperatures in the initial argon atmosphere. Basic trends of the variation in the compositions of the melts and the gas phase above the melts in the presence of carbon are determined. The obtained results characterizing the stability of carbonate components in the melt are analyzed.     

Non-Maxwellian electron energy distribution function in He,He/Ar,He/Xe/H<Subscript>2</Subscript> and He/Xe/D<Subscript>2</Subscript> low temperature afterglow plasma

Experimental studies of the electron energy distribution function “EEDF” under well defined conditions in flowing afterglow plasma, using a Langmuir probe are reported. The EEDF is measured in He₂ ⁺ and Ar⁺ dominated plasmas and in XeH⁺ and XeD⁺ dominated recombining plasmas. He is used as a buffer gas at medium pressures in all experiments (1600 Pa, 250 K). The deviation of the measured EEDF from Maxwellian distribution is shown to depend on plasma composition and on the processes governing the plasma decay. The influence of energetic electrons produced during the plasma decay on the body and tail of the EEDF is observed. The mechanism of energy balance in afterglow plasma is discussed.     

Theoretical study of aging effects on LaNi<Subscript>5</Subscript> tritium storage

The electronic structure and energy of La₂Ni₁₀H₁₂ and La₂Ni₁₀H₁₁He (He is at tetrahedral, octahedral or twelve-face polyhedral interstitials) double cells have been calculated using the density functional theory. Their equilibrium structure, energy bands, electronic density of states (DOS) and X-ray diffraction are presented and discussed. The results indicate the helium-3 produced due to the decay of tritium is most possibly sited at twelve-face polyhedral and octahedral interstices and changes the thermodynamic properties of LaNi₅ tritide system. The changes due to aging such as the reduction in the isotherm plateau pressure, increase of the isotherm plateau slope, and appearance of deeply trapped hydrogen are caused not only by the lattice expansion, but also by modification of the electronic structure due to the presence of He.     

X-Ray Spectral Studies of the Interface Interaction in CuO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/MWCNTs Nanocomposite

Results of a comprehensive study of the interface interaction of a nanostructured CuO_x and multiwalled carbon nanotubes (MWCNTs) in CuO_x/MWCNT nanocomposite by X-ray absorption spectroscopy (XANES, NEXAFS) and X-ray photoelectron spectroscopy (XPS) methods using a synchrotron radiation are presented. It is established that a nanostructured CuO_x in CuO_x/MWCNT nanocomposite is predominantly formed by CuO and has the form of flakelike particles 200–500 nm in size uniformly dispersed over an array of nanotubes. A chemical interaction of CuO_x and nanotubes with formation of covalent carbon–oxygen bonds, which does not lead to a significant destruction of the outer layers of carbon nanotubes, is observed at the interfaces of the nanocomposite.     

Functionalization of multi-walled carbon nanotubes (MWCNTs) with nitrogen plasma for photovoltaic device application

Multi-walled carbon nanotubes (MWCNTs) placed under nitrogen (N₂) and argon (Ar) microwave plasma in order to functionalize covalently their side walls with nitrogen containing groups. X-ray photoelectron spectroscopy (XPS) study shows surface modification of the MWCNTs with imine, amine, nitride and amide groups grafted on the side walls. Due to the functional groups, homogenous distribution of MWCNTs in solvent could be obtained. For photovoltaic device fabrication MWCNTs film was casted over n-Si wafer and poly(3-octylthiophene) solution was infiltered. Devices with functionalized MWCNTs show short circuit current density (J_sc), open circuit voltage (V_oc), fill factor (FF) and power conversion efficiency (η) as 1.8 mA/cm², 0.20 V, 24% and 0.086%, respectively. In the composite film functionalized MWCNTs facilitate photo induced charge separation and efficient holes transportation, suppressing recombination of photo generated charges.     

Plasma polymerization of styrene with carbon dioxide under glow discharge conditions

Plasma polymerization gains increasing interest for the deposition of films with functional properties suitable for a wide range of modern applications on account of its advantageous features. In this study, carbon dioxide (CO₂) was chosen as carrier gas at flow rates of 30 and 60 sccm, respectively and styrene vapor was used as the monomer to prepare polystyrene films on glass substrates. The structure and composition of the plasma polymerized films were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and compared with the film prepared by conventional thermal polymerization. The morphology information of the films was provided by optical microscopy. XPS and FT-IR results reveal that chemical composition of the plasma polymerized films is different from that of the thermal polymerized film and that oxygen content in the plasma polymerized films increases with the flow rate of CO₂. Furthermore, the presence of oxygen-containing groups on the surface of plasma polymerized polystyrene films is confirmed. It is also found that the composition and morphology of the plasma polymerized films are controlled by the flow rate of CO₂.     

Determination of an optimal five-gas combination in a sealed-off CO<Subscript>2</Subscript> laser

For obtaining the maximal output power, five lasing gas mixtures (CO₂, N₂, He, Xe and H₂) in a sealed-off CO₂ laser are optimized by applying a genetic algorithm and solving CO₂ laser kinetics equations. A comparison of numerical simulations shows that the optimal pressures of CO₂ and N₂ are 1.15 Torr and 7.32 Torr, respectively. Accordingly, the maximum laser power of 124 W is obtained by utilizing the optimal gas combination and an optimized resonator with a length of 1.2 m. Received: 14 August 2002 / Published online: 22 January 2003 The project supported by Zhejiang Provincial Natural Science Foundation of China (No. 602098). RID="*" ID="*"Corresponding author. Fax: +86-571/8832-0369, E-mail: chengch@mail.hz.zj.cn     

Electric-discharge He/Xe/I<Subscript>2</Subscript> excimer-halogen UV lamp

The characteristics of a low-size low-pressure UV lamp operating on the atomic iodine resonant line (λ=206 nm) and xenon iodide (λ=253 nm) and dimer iodine (λ=342 nm) bands are investigated. A lamp with an interelectrode distance of 19 cm was pumped by a longitudinal dc glow discharge. The working gas mixtures were He/I₂ and He/Xe/I₂ mixtures with a total pressure of 50–1500 Pa. The output parameters of the electric-discharge excimer-halogen lamp were optimized in terms of the gas mixture pressure and composition and the power deposited in the discharge. It is shown that the total UV power emitted from the entire aperture of the lamp in the spectral range 200–350 nm attains 5–7 W with an efficiency of ≤5%.     

Spontaneous generation of electric voltage in a single crystal of Sm<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3</Subscript>

Spontaneous generation of electric voltage has been found in a Sm_0.55Sr_0.45MnO₃ single crystal grown by floating zone melting with cooling in oxygen. The maximum voltage of 60 μV has been observed in the region of temperatures corresponding, simultaneously, to destruction of the CE-type antiferromagnetic ordering and charge ordering in some clusters. The maximum voltage remains unchanged for 24 h and decreases by 45% in a magnetic field of 14.2 kOe. It has been shown that the spontaneous voltage is caused by the presence of regions with different electric charges in the sample.     

A miniature tunable TEA CO<Subscript>2</Subscript> laser using isotope <Superscript>13</Superscript>C<Superscript>16</Superscript>O<Subscript>2</Subscript> and <Superscript>12</Superscript>C<Superscript>16</Superscript>O<Subscript>2</Subscript>

A miniature tunable TEA CO₂ laser using isotope ¹³C¹⁶O₂ as the active medium is developed to extend the spectral range of CO₂ lasers for further application. The optimization of the energy parameters of the tunable TEA ¹³C¹⁶O₂ laser and the same laser using ¹²C¹⁶O₂ are studied. When a gas mixture (¹³C¹⁶O₂: N₂: He = 1: 1: 3) at a total pressure of 6.4 × 10⁴ Pa is used, the TEA ¹³C¹⁶O₂ laser of a 45-cm³ active volume obtains 51 emission lines in the [00⁰1–10⁰0] and [00⁰1–02⁰0] bands. The maximum pulse energy of the TEA ¹³C¹⁶O₂ laser is about 357 mJ. The same laser using the conventional gas mixture (¹²C¹⁶O₂: N₂: He = 1: 1: 3) at a pressure of 6.66 × 10⁴ Pa is measured to obtain 69 laser emission lines and the maximum pulse energy of laser radiation is about 409 mJ.     

EPR spectra of aerosol particles formed by pyrolysis of C<Subscript>3</Subscript>H<Subscript>8</Subscript> plus Ar and C<Subscript>3</Subscript>H<Subscript>8</Subscript> plus Fe(CO)<Subscript>5</Subscript> plus Ar mixtures in a flow reactor

The paper is devoted to electron paramagnetic resonance investigation of nanoparticles and aggregates of nanoparticles formed by pyrolysis of propane as well as a mixture of propane and iron pentacarbonyl. The measurement showed that the pyrolysis of the C₃H₈ plus Ar mixture results in the formation of a carbonaceous phase (phase I), which is quite different from that formed by the C₃H₈ plus Fe(CO)₅ plus Ar mixture (phase II). In phase I there is a strong oxygen effect for as-prepared samples; 75% of spins are accessible to the environmental gas via the interconnected system of microvoids and microchannels. In phase II there was a weak oxygen effect for the as-prepared samples. However, after exposition of phase II to air for 160 h, the properties of phase II have become about the same as that of phase I. A strong oxygen effect was observed for the air-exposed phase II. The line width for phase II increases monotonically with the iron content in the sample. This increase is probably related to the dipole-dipole interactions between the radical centers and the iron atoms distributed throughout the carbon matrix.     

Effect of carbon coating process on the structure and electrochemical performance of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>O<Subscript>2</Subscript> used as cathode in Li-ion batteries

LiNi_0.5Mn_0.5O₂ powder was synthesized by a coprecipitation method. LiOH.H₂O and coprecipitated [(Ni_0.5Mn_0.5)C₂O₄] precursors were mixed carefully together and then calcined at 900°C. Surface modified cathode materials were obtained by coating LiNi_0.5Mn_0.5O₂ with a thin layer of amorphous carbon using table sugar and starch as carbon source. Both parent and carbon-coated samples have the characteristic layered structure of LiNi_0.5Mn_0.5O₂ as estimated from X-ray diffractometry measurements. Transmission electron microscope showed the presence of C layer around the prepared particles. TGA analysis emphasized and confirmed the presence of C coating around LiNi_0.5Mn_0.5O₂. It is obvious that the carbon coating appears to be beneficial for the electrochemical performance of the LiNi_0.5Mn_0.5O₂. A capacity of about 150 mAh/g is delivered in the voltage range 2.5–4.5 V at current density C/15 for carbon coated LiNi_0.5Mn_0.5O₂ in comparison with about 165 mAh/g obtained for carbon free LiNi_0.5Mn_0.5O₂ at the same current density and voltage window. About 92% and 82% capacity retention was obtained at 50th cycle for coated LiNi_0.5Mn_0.5O₂ using sucrose and starch, respectively; whereas, 75% was retained after only 30th cycle for carbon free LiNi_0.5Mn_0.5O₂. This improvement is mainly attributed to the presence of thin layer of carbon layer that encapsulate the nanoparticles and improve the conductivity and the electrochemical performance of LiNi_0.5Mn_0.5O₂.