Carbon nanotube diameter tuning using hydrogen amount and temperature on SiO2/Si substrates

Carbon nanotubes (CNTs) were grown on thin iron (Fe) films on SiO₂/Si substrates by chemical vapor deposition (CVD) at four different hydrogen (H₂)/methane (CH₄) ratios at temperatures ranging from 925 to 1000°C. The effects of temperature and the amount of hydrogen gas on the mean diameter at increasing temperature were examined. We demonstrated that the mean diameter and its distribution depend not only on temperature but also on the H₂ amount. We showed that increasing H₂ amount strongly affects the structure of CNTs, especially at high growth temperature; the mean diameter at 1000°C reduced from about 383 to 34 nm by increasing H₂ amount from 24 to 50 sccm. We observed that at high temperature growth the mean diameter was decreasing very fast initially with increasing H₂ amount suggesting the dominance of H₂ over the growth temperature. A decrease in the slope of diameter vs. H₂ amount with further increment in H₂ amount implied that the temperature was, then, deciding the CNT diameter through catalyst particle coarsening. The statistical analysis presented implies that the H₂ amount has to be adjusted according to the growth temperature for given CH₄ amount to keep CNT diameter under control, and the large diameter distributions at high temperature and high H₂ amount can be associated with the large variation in the catalyst particle sizes.     

Study of temperature variations of NMR spectra in monohydrates FeSO4. 1 H2O and MgSO4. 1 H2O

The paper deals with a study of the proton nuclear magnetic resonance (NMR) of crystallization water in isomorphous monohydrates MgSO₄. 1 H₂O and FeSO₄. 1 H₂O in the temperature range 123–313 K. The NMR second moment for diamagnetic MgSO₄. 1 H₂O shows only a weak dependence on temperature but the one for paramagnetic FeSO₄. 1 H₂O is rather strong. Results obtained for FeSO₄. 1 H₂O are in a good agreement with the Kroon's theory of NMR in paramagnetics. The Curie-Weiss constant and the effective magnetic moment of Fe²⁺ ions in FeSO₄. 1 H₂O are derived from the temperature dependence of NMR second moment. The motion of molecules of crystallization water in these hydrates is discussed on the basis of temperature dependences of the width and second moment of NMR spectra.     

UV raman spectroscopy of H2-air flames excited with a narrowband KrF laser

Raman spectra of H₂ and H₂O in flames excited by a narrowband KrF excimer laser are reported. Observations are made over a porous-plug, flat-flame burner reacting H₂ in air, fuel-rich with nitrogen dilution to control the temperature, and with a H₂ diffusion flame. Measurements made from UV Raman spectra show good agreement with measurements made by other means, both for gas temperature and relative major species concentrations. Laser-induced fluorescence interferences arising from OH and O₂ are observed in emission near the Raman spectra. These interferences do not preclude Raman measurements, however.     

The chemisorption of CO,CO2, C2H2, C2H4, H2 and NH3 on the clean Fe(100) and (111) crystal surfaces

The chemisorption of small molecules (CO, CO₂, C₂H₂, C₂H₄, H₂ and NH₃) has been studied on the clean Fe(110) and (111) crystal faces by low-energy electron diffraction (LEED) and thermal desorption. C₂H₄ and C₂H₂ yield the same sequence of surface structures that change with temperature and crystal orientation. CO and CO₂ chemisorption similarly results in the formation of the same types of surface structures that change with surface temperature and crystal orientation. Ammonia forms several ordered surface structures on both iron crystal faces. All of the molecules decompose as a function of temperature on the iron surfaces as indicated by the Auger and thermal desorption spectra.     

Near-infrared diode laser absorption sensor for rapid measurements of temperature and water vapor in a shock tube

A fast-response (100 kHz) tunable diode laser absorption sensor is developed for measurements of temperature and H₂O concentration in shock tubes, e.g. for studies of combustion chemistry. Gas temperature is determined from the ratio of fixed-wavelength laser absorption of two H₂O transitions near 7185.60 cm^-1 and 7154.35 cm^-1, which are selected using design rules for the target temperature range of 1000–2000 K and pressure range of 1–2 atm. Wavelength modulation spectroscopy is employed with second-harmonic detection (WMS-2f) to improve the sensor sensitivity and accuracy. Normalization of the second-harmonic signal by the first-harmonic signal is used to remove the need for calibration and minimize interference from emission, scattering, beam steering, and window fouling. The laser modulation depth for each H₂O transition is optimized to maximize the WMS-2f signal for the target test conditions. The WMS-2f sensor is first validated in mixtures of H₂O and Ar in a heated cell for the temperature range of 500–1200 K (P=1 atm), yielding an accuracy of 1.9% for temperature and 1.4% for H₂O concentration measurements. Shock wave tests with non-reactive H₂O–Ar mixtures are then conducted to demonstrate the sensor accuracy (1.5% for temperature and 1.4% for H₂O concentration) and response time at higher temperatures (1200–1700 K, P=1.3–1.6 atm). PACS 42.62.Fi; 42.55.Px; 42.60.Fc; 07.35.+k     

Hydrogen CARS thermometry in a high-pressure H2–air flame. Test of H2 temperature accuracy and influence of line width by comparison with N2 CARS as reference

This work describes a further step towards the determination of the temperature accuracy of H₂ Q-branch CARS (Coherent Anti-Stokes Raman Scattering) at high pressure with regard to the influence of the H₂ line widths. In laminar steady H₂/air flames in the pressure range 1–15 bar and at fuel-rich conditions with stoichiometries between two and four, quasi-simultaneous temperature measurements were performed with H₂ and N₂ CARS. The temperature values deduced from H₂ CARS are in good agreement with the reference temperature from N₂ CARS. The influence of different line-width contributions on the accuracy of H₂ Q-branch thermometry was investigated in detail. Received: 10 April 2001 / Revised version: 22 May 2001 / Published online: 18 July 2001     

Adsorption of H2O on Al(111)

The adsorption of H₂O on Al(111) has been studied by ESDIAD (electron stimulated desorption ion angular distributions), LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and thermal desorption in the temperature range 80–700 K. At 80 K, H₂O is adsorbed predominantly in molecular form, and the ESDIAD patterns indicate that bonding occurs through the O atom, with the molecular axis tilted away from the surface normal. Some of the H₂O adsorbed at 80 K on clean Al(111) can be desorbed in molecular form, but a considerable fraction dissociates upon heating into OH_ads and hydrogen, which leaves the surface as H₂. Following adsorption of H₂O onto oxygen-precovered Al(111), additional OH_ads is formed upon heating (perhaps via a hydrogen abstraction reaction), and H₂ desorbs at temperatures considerably higher than that seen for H₂O on clean Al(111). The general behavior of H₂O adsorption on clean and oxygen-precovered Al(111) (θ_O ? monolayer) is rather similar at low temperature, but much higher reactivity for dissociative adsorption of H₂O to form OH _adsis noted on the oxygen-dosed surface around room temperature.     

ZnO-Fe3O4 composite prepared by sol-gel method with H2 deoxidation

Fe doped ZnO powder samples (Fe/Zn=0.05 and 0.1) were prepared by sol-gel method with H₂ deoxidation at 450 ^°C for several hours or just heated in air at the same temperature. It was showed by vibrating sample magnetometer (VSM) that samples heat treated in H₂ could show strong ferromagnetism at room temperature while samples treated in air only show very weak magnetism. XRD using Co kα X-ray revealed that the samples heated in H₂ were not pure phase but like a granular system and the magnetism mainly results from Fe₃O₄ in samples while samples heated in air showed pure ZnO phase. Our work indicated that H₂ deoxidation treatment may be an effective technique to fabricate such magnetic semiconductor-like materials with Curie temperature higher than room temperature.     

Dielectric behaviour of α-cyclodextrin,heptakis (2,3,6-tri-Omethyl)-β-cyclodextrin,randomly methylated β-cyclodextrin and low frequency Raman spectra of α- and β-cyclodextrins

The frequency and temperature dependence of the real (?′) and imaginary (?″)parts of the dielectric constant of α-cyclodrextrin (form 1; α-CD. 5.9H₂O) and α-cyclodextrin (form III; α-CD.7.6H₂O) and of the corresponding dried forms (α-CD.1.1H₂O, α-CD.2.9H₂O, respectively) has been investigated over the frequency range 0–100 k Hz and temperature range 130–350 K. In addition the dielectric behaviour has been investigated of heptakis-(2,3,6-tri-O-methyl)-β-cyclodextrin (β-CD.TRIME. 0.3H₂O) and randomly methylated β-cyclodextrin (β-CD.RAME.0.8H₂O). The dielectric behaviour is described well by Debyetype relaxation (α-disperson). All α-CD systems exhibit an additional ω-dispersion at low frequencies, which is attributed to proton transport. The fact that the ?′ values of α-CD form III are larger than those of α-CD form I is attributed to the different numbers and different strengths of the intramolecular hydrogen bonds. Form III has a stable conformation which is shown by the constant values of ?′ in the temperature range 125–250 K. By contrast, in form I the ?′ values increased linearly with temperature, indicating that the system passed through succesive conformations. The temperature dependence of ?″ and phase shift ∞ in all the specimens of α-CD (forms I, III) and fully methylated β-CD do not reveal any orderdisorder transition, because the developed hydrogen bonds ae not of the flip-flop type according to their crystal structures. The partially methylated β-CD reveals the characteristics of the order-disorder transition, which was observed before in the systems dried β-CD.2H₂O and non-dried β-CD.9.8H₂O. There is a direct relation between the hydroxyl groups of β-CD and the order-disorder transition. The order-disorder transition could also be shown in dried β-CD.2.4H₂O and non-dried β-CD.9.8H₂O samples but not in dried α-CD.1.1H₂O and non-dried a-CD.5.9H₂O samples, by low frequency Raman spectroscopy (< 180 cm^?1). The step-like temperature dependence of the band at 33.7cm^?1 reveals a transition at about 223K for both β-CD samples. In the case of α-CD samples the almost linear temperature dependence of the band at 49.1 cm^?1 does not reveal any transition.     

Kinetics of low-temperature initiation of H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/H<Subscript>2</Subscript>O mixture combustion upon the excitation of molecular vibrations in H<Subscript>2</Subscript>O molecules by laser radiation

The initiation of H₂/O₂/H₂O mixture combustion when asymmetric vibrations in H₂O molecules are excited by a resonant IR laser radiation is considered. It is shown that the vibrational excitation of the molecules gives rise to new efficient channels for the formation of chemically active O and H atoms and OH radicals. As a result, the chain mechanism of combustion in the mixtures is enhanced and, as a consequence, the induction time is cut and the ignition temperature is lowered. Even at a minor radiant energy flux delivered to the gas (E_in≈2.5 J/cm²), the ignition temperature of the stoichiometric H₂/O₂ mixture containing only 5% of H₂O may become as low as 300 K.     

Absorption measurements of H2O at high temperatures using a CO laser

Absorption of CO laser radiation (v = 8→7, J = 14→15 transition at 1901.762 cm^-1) by H₂O has been studied in shock-heated H₂/O₂/Ar mixtures over the temperature range 1300–2300 K. This laser transition is nearly coincident with the v₂-band 12_3,10←11_2,9 transition of H₂O at 1901.760 cm^-1, thereby providing a convenient and sensitive absorption-based H₂O diagnostic useful for studies of combustion. The collision-broadening parameter for this H₂O line, due to broadening by Ar, was determined to be 2γ (cm^-1atm^-1) = 0.027 (T/1300)^-0.9 in the temperature range 1300–2300 K. Calculations of the H₂O absorption coefficient (at 1901.762 cm^-1) based on this expression for 2γ are presented for the temperature range 300–2500 K and pressure range 0.3–1 atm.     

Scanned-wavelength-modulation spectroscopy near 2.5 μm for H2O and temperature in a hydrocarbon-fueled scramjet combustor

The design and demonstration of a two-color tunable diode laser sensor for measurements of temperature and H₂O in an ethylene-fueled model scramjet combustor are presented. This sensor probes multiple H₂O transitions in the fundamental vibration bands near 2.5 μm that are up to 20 times stronger than those used by previous near-infrared H₂O sensors. In addition, two design measures enabled high-fidelity measurements in the nonuniform flow field. (1) A recently developed calibration-free scanned-wavelength-modulation spectroscopy spectral-fitting strategy was used to infer the integrated absorbance of each transition without a priori knowledge of the absorption lineshape and (2) transitions with strengths that scale near-linearly with temperature were used to accurately determine the H₂O column density and the H₂O-weighted path-averaged temperature from the integrated absorbance of two transitions.     

Ullah-Dorsey Scaling of Fluctuation Conductivity Near the Superconducting Transition in (LaSe)1.14(NbSe2)

Magnetotransport measurements with the quasi two-dimensional misfit-layer compound (LaSe)_1.14(NbSe₂) with critical temperature T _c = 1.23 K are presented. The temperature dependence of the upper critical magnetic field H _c2 has been determined from an analysis of magnetoresistance data through the scaling procedure obtained theroretically by Ullah and Dorsey for the fluctuation conductivity. We show that in contrast to a direct determination of H _c2(T) with a positive curvature the temperature dependence of H _c2 obtained via the scaling procedure reveals a negative curvature in agreement with the Werthammer-Helfand-Hohenberg theory for conventional type-II superconductors.     

Phase diagram for diamond growth in atmospheric oxyacetylene flames

2 /C₂H₂ ratio for diamond synthesis in oxyacetylene flames can be theoretically predicted. When the substrate temperature is between 1000 K and 1250 K, the corresponding O₂/C₂H₂ ratio range is about between 0.8 and 1.1. The suitable range of substrate temperature is widest for O₂/C₂H₂ ratio close to unity and is narrowed rapidly when the flow ratio deviates from unity. Received: 2 March 1997/Accepted: 17 July 1997     

Collisional broadening and shifting of the 211-202 transition of H2O, H2O, H2O by atmosphere gases

Broadening and shifting of the 2₁₁-2₀₂ transition of H₂¹⁶O, H₂¹⁷O, H₂¹⁸O by pressure of water, nitrogen and oxygen were precisely measured at room temperature using spectrometer with radio-acoustic detection of absorption. Shift parameters for all studied lines as well as broadening parameters of H₂¹⁷O, H₂¹⁸O lines were measured for the first time. Comparison of obtained results with previously known experimental and theoretical data is presented.     

Optical diagnostic of temperature in rocket engines by coherent Raman techniques

This article reviews the study of Raman line shapes of molecular species involved in reactive media, such flames or engines, at high temperature and high pressure. This study is of interest from a fundamental as well as from a practical point of view with regards to the CARS temperature diagnostic of GH₂–LOX combustion systems. We will particularly draw attention to recent investigations by means of Stimulated Raman Spectroscopy (SRS) in H₂–H₂O mixtures at temperature up to 1800 K. Whereas H₂–X systems usually exhibit large inhomogeneous effects, due to the speed dependence of the collisional parameters, the absence of such apparent inhomogeneous signatures in the H₂–H₂O system allowed us to model the broadening coefficients with simple polynomial laws. These laws permit extrapolations with a narrow confidence interval, as required for temperature measurements. The applications of these results to the temperature diagnostic on the small-scale facility MASCOTTE at ONERA will be described. To cite this article: F. Chaussard et al., C. R. Physique 5 (2004).     

Electrical conductivity and chemical diffusion in Perovskite-type proton conductors in H2-H2O gas mixtures

The electrical conductivities of SrZr_0.9Y_0.1O_3-δ (SZY10) and BaCe_0.95Y_0.05O_3-δ(BCY5) were measured as a function of hydrogen partial pressure P(H₂), oxygen partial pressure P(O₂), steam partial pressure P(H₂O) and temperature. Their relaxation processes were analyzed using the solution of Fick's diffusion equation to determine the chemical diffusion coefficients and surface reaction rate constants. There were the differences in chemical relaxation kinetics and the conductivity dependence on P(H₂O) between the both oxides. The chemical diffusion coefficients depend on temperature but are essentially independent of P(H₂), P(O₂) and P(H₂O). The ambipolar diffusion treatment can explain the temperature dependence of chemical diffusion coefficients quantitatively. The chemical diffusion coefficients of SZY10 is one or two order of magnitude smaller than those of BCY5 at low temperature. The sluggish conductivity relaxation in SZY10 was due to considerably small oxygen vacancy diffusion coefficients at low temperatures. The total conductivity depends on P(H₂O) in the case of SZY10, but not for BCY5. This different dependence on P(H₂O) is caused by the difference in the ratio between proton mobility and oxide-ion mobility.     

Influence of temperature on critical fields in ZnCr2Se4

The complex ac dynamic magnetic susceptibility was used to study the influence of temperature on critical fields in polycrystalline ZnCr₂Se₄ spinel. An antiferromagnetic order with a Néel temperature T_N=20.7 K and a strong ferromagnetic exchange evidenced by a positive Curie-Weiss temperature θ_CW=55.1 K were established. An increasing static magnetic field shifts T_N to lower temperatures while a susceptibility peak at T_m in the paramagnetic region—to higher temperatures. The non-zero and negative values both of the second and third harmonics of susceptibility suggest only a parallel spin coupling in ferromagnetic clusters in the range between the Néel and Curie-Weiss temperatures. Below T_N the magnetic field dependence of susceptibility, χ_ac(H), shows two peaks at critical fields H_c1 and H_c2. The values of H_c1 decrease slightly with temperature while the values of H_c2 drop rapidly with temperature. The strong changes of H_c2 temperature induced are mainly responsible for a spin frustration of the re-entrant type in the spinel under study.     

H2 oxidation on Ni/Y–TZP cermet electrodes – polarisation behaviour

The polarisation behaviour of Ni/3 mol % Y₂O₃–ZrO₂ (Ni/Y–TZP) cermet electrodes for H₂ oxidation reaction has been investigated by the galvanostatic current interruption (GCI) over a wide range of H₂O content and temperature in both undiluted and diluted H₂ fuel. The electrode performance increases with H₂O content with a maximum at 14% H₂O. The reaction orders with respect to partial pressure of H₂O and H₂ are 0.5 and 0.1, respectively. The activation energy for the reaction is about 70 kJ mol⁻¹ in the H₂O content range between 4 to 14% in undiluted H₂ and in the H₂ content range between 14 to 96% in diluted H₂. The polarisation behaviour was analysed by fitting the measured data with the Nernst-type concentration equation and an empirical rate equation. The results have demonstrated that charge transfer process may play an very important role in the polarisation behaviour for H₂ oxidation reaction on Ni/Y–TZP cermet electrodes. The deviation of the calculated data according to the empirical rate equation from the measured polarisation data at high current densities and low H₂ contents indicates that the reaction is limited by at least two electrode processes.     

C2H4在清洁和有Cs覆盖的Ru(0001)表面吸附的TDS研究

用热脱附谱(TDS)方法研究了乙烯(C₂H₄)在Ru(0001)表面上的吸附.在低温下(200K以下)乙烯可以在清洁及有Cs的Ru(0001)表面上以分子状态稳定吸附,在衬底温度升高至200K以上时,乙烯发生了脱氢分解反应,乙烯分解后的主要产物为乙炔(C₂H₂).在清洁的Ru(0001)表面,乙烯有两种吸附状态,脱附温度分别为275K和360K.而乙炔的脱附温度为350K.在Ru(0001)表面有Cs的存在时,乙烯分解 关键词： 乙烯 钌(0001)表面 铯钌(0001)表面乙烯 钌(0001)表面 铯钌(0001)表面