X-ray absorption of nitrogen-doped amorphous carbon films for determining sp2/sp3 bonding concentrations

A method of analyzing X-ray absorption spectra of nitrogen-doped amorphous carbon (a-C) samples was developed to determine their sp² bonding concentrations. The films under consideration are simultaneously deposited onto polytetrafluoroethylene (PTFE) polymer or silicon wafer substrates by hot wire plasma sputtering of graphite. sp² bonding concentrations of a-C films deposited on PTFE increase from 74% to 93% with growing nitrogen doping. Silicon substrate films yield the same general trend, but show that the near surface electronic structure of a-C films depends on the substrate.     

Good electrical and mechanical properties induced by the multilayer graphene oxide sheets incorporated to amorphous carbon films

Multilayer graphene oxide nanosheets were fabricated using commercially available expanded graphite by simple ultrasonic treatment and then were incorporated into the amorphous carbon matrix as fillers by electrochemical deposition. The electrical conductivity of the films was strongly improved due to the contribution of the multilayer graphene oxide sheets. Moreover, the Young’s modulus, hardness and elastic recovery of the composite films were measured to be about 171.1 GPa, 10.1 GPa and 81.4%, respectively, compared to 137.4 GPa, 5.1 GPa and 44.3% of undoped a-C:H films prepared at the same conditions. Additionally, the friction coefficient was tested to be 0.15 (0.5 N, 2 Hz) and the antiwear life was prolonged to about 200 s while the undoped DLC films obtained at the same condition were easy to be frazzled.     

Kinetics of the NCO + HCNO reaction

The kinetics of the NCO + HCNO reaction were studied using infrared diode laser absorption spectroscopy. The total rate constant was measured to be k(1) = (1.58 +/- 0.20) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K. After detection of products and consideration of secondary chemistry (primarily O + HCNO and CN + HCNO), we conclude that NO + CO + HCN is the major product channel (phi = 0.92 +/- 0.04), with a minor contribution (phi = 0.04 +/- 0.02) from CO2 + HCNN.     

大功率激光制备a-C和a-C∶H类金刚石膜的光学性能研究

采用大功率高重复频率准分子激光溅射热解石墨靶制备了类金刚石碳膜, 研究了实验条件对类金刚石膜光学性能的影响, 发现氢可以提高膜中sp3键的含量和膜的光学透过率. 在实验参数范围内, 膜的光学性能随着氢压的增加而提高. 根据类金刚石膜的反应沉积机理对上述结果进行了分析、解释.     

Preparation of films from aluminum acetylacetonate by plasma sputtering

Aluminum acetylacetonate has been reported as a precursor for the deposition of alumina films using different approaches. In this work, alumina‐containing films were prepared by plasma sputtering this compound, spread directly on the powered lowermost electrode of a reactor, while grounding the substrates mounted on the topmost electrode. Radiofrequency power (13.56 MHz) was used to excite the plasma from argon atmosphere at a working pressure of 11 Pa. The effect of the plasma excitation power on the properties of the resulting films was studied. Film thickness and hardness were measured by profilometry and nanoindentation, respectively. The molecular structure and chemical composition of the layers were analyzed by Fourier transform infrared spectroscopy and energy dispersive spectroscopy. Surface micrographs, obtained by scanning electron microscopy, allowed the determination of the sample morphology. Grazing incidence X‐ray diffraction was employed to determine the structure of the films. Amorphous organic layers were deposited with thicknesses of up to 7 µm and hardness of around 1.0 GPa. The films were composed by aluminum, carbon, oxygen and hydrogen, their proportions being strongly dependent on the power used to excite the plasma. A uniform surface was obtained for low‐power depositions, but particulates and cracks appeared in the high‐power prepared materials. The presence of different proportions of aluminum oxide in the coatings is ascribed to the different activations promoted in the metalorganic molecule once in the plasma phase. Copyright © 2013 John Wiley & Sons, Ltd.     

Optical emission spectroscopy in reactive hollow cathode arc discharge plasmas – Local distribution of active species during the deposition of hard carbon films

A low pressure arc plasma discharge from a hollow LaB(6)-cathode with up to 100 A discharge current is used to create plasmas of high density. Typical values for the electron density and temperature in PETRA ( Plasma Engineering and Technology Research Assembly) are n(e)=10(12)-10(13) cm(-3) and T(e)=5-20 eV. The ionization ratio is typically 1-10%. Optical emission spectroscopy has been applied to investigate the processes within the plasma which lead to the deposition of thin carbon films. In these experiments hydrogenated carbon films (a-C:H) have been deposited on Si-substrates by introducing hydrocarbon gases (CH(4), C(2)H(2)) into He- and Ar-plasmas. Space resolved optical emission spectroscopy using an in-situ translation mechanism of the optical fibre has been performed to measure the local concentrations of CH-radicals, carbon ions and of the excitation of He-neutrals. In addition the hydrogen liberated by the dissociation of the hydrocarbon molecules has been measured. The dissociation of the hydrocarbon molecules takes place as a localized process in the vicinity of the reactive gas inlet.     

Kinetic Analyses of Colloidal Crystallization in a Wide Range of Sphere Concentrations as Studied by Reflection Spectroscopy

The nucleation and growth rates in the colloidal crystallization of silica spheres (103 nm in diameter) from 0.006 to 0.04 in volume fraction (straight phi) have been measured by reflection spectroscopy. Kinetics of the crystallization has been discussed in a wide sphere concentration range (from straight phi=0.0005 to straight phi=0.04) using the data of this work and the previous work (110 nm in diameter) in exhaustively deionized aqueous suspensions. The induction period for nucleation decreases sharply as the sphere concentration increases. The nucleation rate increases substantially from 1x10(-3) to 1x10(7) mm(-3) s(-1) when straight phi increases from 0.0005 to 0.04. The crystal growth process consists of the fast growing step toward metastable crystals (rate v(1)) and slow growth accompanied with the reorientation toward stable ones (rate v(2)). The v(1) values increase first from 5 to 20 μm/s and then turn back to 5 μm/s after passing a maximum. v(1) above straight phi=0.01 remains at 5 μm/s and is insensitive to sphere concentration. The slow step is observed in the high-sphere concentrations only, and v(2) decreases sharply from 3 μm/s to 0.7 nm/s when sphere concentration increases from 0.004 to 0.04 in volume fraction. Importance of the electrostatic intersphere repulsion by overlapping of the electrical double layers and the cooperative and synchronized fluctuation of colloidal spheres in the crystallization processes are supported strongly. Copyright 2000 Academic Press.     

Structure evolution of hydrogenated carbon films from amorphous carbon to fullerene‐like nanostructure

A–C:H (hydrogenated amorphous carbon) films were deposited by pulsed direct‐current (d.c.) plasma enhanced chemical vapor deposition on silicon substrates. This study investigated the structural and mechanical evolution of the as‐deposited films with fullerene‐like nanostructure. The results showed that pulsed d.c. negative bias (?500 ~ ?1000 V) signally influenced the growth rate, hardness, surface roughness, sp³ content, and friction behavior of the films. As the pulsed d.c. negative bias voltage increased, the sp³ content, surface roughness, hydrogen content and the friction coefficient of the films decreased; however, the growth rate and the hardness increased. The films deposited at ?1000 V with fullerene‐like microstructure display a nanohardness of about 19.7 GPa and the smallest friction coefficient (~0.06). The evolution on mechanical and structural properties of the films are explained by the a–C:H growth mechanism based on the interaction on plasma‐surface interface and the subsurface reactions in the film. Copyright © 2014 John Wiley & Sons, Ltd.     

等离子体增强磁控溅射沉积碳化硅薄膜的化学结构与成膜机理

以CH4和Ar为工作气体,单晶硅为溅射靶,通过微波电子回旋共振(MW-ECR)等离子体增强非平衡磁控溅射方法在不同的CH4流量和沉积温度下制备了a-Si1-xCx∶H薄膜.利用傅里叶变换红外(FT-IR)光谱,X光电子能谱(XPS)和纳米硬度仪等表征方法研究不同沉积参数下薄膜的化学结构、化学配比和硬度的变化.结果表明:室温(25℃)下随CH4流量由5cm·3min-1增加到45cm3·min-1(标准状态)时,薄膜中Si—CH2键,C—H键含量逐渐增加,Si—H键变化不明显;膜中C原子百分比由28%增至76%,Si原子百分比由62%降至19%.当CH4流量为15cm3·min-1时,随沉积温度的升高,薄膜中Si和C原子百分比含量分别为52%和43%,且基本保持不变;膜中Si—H键和C—H键转化为Si—C键,薄膜的显微硬度显著提高,在沉积温度为600℃时达到29.7GPa.根据分析结果,提出了室温和高温下a-Si1-xCx:H薄膜生长模型.     

Electrochemical properties of amorphous nitrogen-containing hydrogenated diamondlike-carbon films

The electrochemical impedance of thin-film electrodes made of amorphous nitrogen-containing diamondlike carbon (a-C:N:H) in H₂SO₄ solutions and the kinetics of redox reactions on these electrodes in the Fe(CN) ₆ ^3-/4- system are studied. The amorphous diamondlike carbon films with an admixture of nitrogen are grown by a directed deposition from inductively coupled methane-nitrogen plasma. The films’ resistivity values determined from the ac impedance of a-C:N:H/electrolyte contact practically coincided with those determined from the current-vol.tage curves taken at the a-C:N:H/metal contact. With an increase in the nitrogen : methane ratio in the gas phase, both the electrical resistance and optical bandgap decrease from 3 x 10¹⁰ to 5 x 10⁶ ohm cm and from 1.3 to 0.6 eV, respectively. Simultaneously, the concentration of electrically active point-defect centers in a-C:N:H increases significantly and the reaction in the Fe(CN) ₆ ^3-/4- system is facilitated.     

Structure,Composition, Mechanical,and Tribological Properties of BCN Films Deposited by Plasma Enhanced Chemical Vapor Deposition

In this work thin BCN films were deposited by plasma enhanced chemical vapor deposition (PECVD) using chloridic precursors. Through adjusting the BCl₃ content in the inlet gas mixture the chemical composition of the deposited films was changed from carbon rich to boron rich. Based on optical emission spectroscopy (OES) measurements, a correlation between film composition and precursor species concentration in the plasma was established. The films were amorphous as detected by grazing incidence X-ray diffraction (GIXRD). The hardness and the elastic modulus have maximal values of 25.5±1.2 and 191±6 GPa, respectively, for the films with a boron concentration of 45.2 at.%. GIXRD data suggest that a depletion in boron content may initiate the formation of graphitic domains in the amorphous matrix. The observed degradation of the mechanical properties is associated with the graphitization. The tribological behavior was studied with a tribometer operated in pin-on-plate configuration at the temperatures 25 and 400°C. The wear mechanisms were discussed with respect to the formation of a boric acid surface layer which was detected by reflection electron energy loss spectroscopy (REELS) analysis.     

Characteristics of Ti–Nb,Ti–Zr and Ti–Al containing hydrogenated carbon nitride films

Nanocomposite Me–C–N:H coatings (Me is TiNb, TiZr or TiAl), with relatively high non-metal/metal ratios, were prepared by cathodic arc method using TiNb, TiZr and TiAl alloy cathodes in a CH₄ + N₂ atmosphere. For comparison purposes, a-C–N:H films were also produced through evaporating a graphite cathode in a similar atmosphere. The films were characterized in terms of elemental and phase compositions, chemical bonds, texture, hardness, adhesion and friction behavior by GDOES, XPS, Raman spectroscopy and XRD techniques, surface profilometry, hardness and scratch adhesion measurements, and tribological tests. The nanocomposite films consisted of a mixture of crystalline metal carbonitride and amorphous carbon nitride. The non-metal/metal ratio in the films composition was found to range between 1.8 and 1.9. For the metal containing nanocomposites, grain size in the range 7–23 nm, depending on the metal nature, were determined. As compared with the a-C–N:H, the Me–C–N:H films exhibited a much higher hardness (up to about 39 GPa for Ti–Zr–C–N:H) and a better adhesion strength, while the coefficients of friction were somewhat higher (0.2–0.3 for Me–C–N:H and 0.1 for a-C–N:H).     

Achieving ultra-low friction of a-C:H film grown on 9Cr18Mo steel for industrial application via programmable high power pulse magnetron sputtering

Owing to the high hardness and hydrogen passivation of carbon bonds, hydrogenated diamond-like carbon (a-C:H) film has shown promising potential to achieve ultra-low friction and wear on steel surfaces. Here, a-C:H film was successfully deposited on 9Cr18Mo steel via programmable high power pulse magnetron sputtering and potential application for industrial was evaluated. The a-C:H films against different mating materials of GCr15 steel balls, Al₂O₃, Si₃N₄, ZrO₂, and a-C:H-coated GCr15 balls all showed ultra-low friction under a normal load of 5 N in a dry ambient air environment. Among them, self-mating tribo-system a-C:H films on steel surfaces and a-C:H-coated steel balls achieve best friction performance; the principal reason is that both contacting surfaces coated with a-C:H film have the lower electron affinities compared with other tribo-systems. However, the differences of coefficient of friction (COF) for uncoated-GCr15, Al₂O₃, ZrO₂, Si₃N₄, and a-C:H(GCr15) balls can be attributed to different sizes of clustering in wear debris. This work provides new insights on synthesis and industry application of the a-C:H films with ultra-low friction properties.     

Influence of deposition pressure on hydrogenated amorphous carbon films prepared by d.c.‐pulse plasma chemical vapor deposition

Hydrogenated amorphous carbon films (a‐C : H) were prepared by d.c.‐pulse plasma chemical vapor deposition using CH₄ and H₂ gases. The microstructure and hardness of the resulting films were investigated at different deposition pressures (6, 8, 11, 15, and 20 Pa). The growth rate increased sharply from 3.2 to 10.3 nm/min with increasing the pressure from 6 to 20 Pa. According to Raman spectra, XPS, and Fourier transform infrared analysis, the films deposited at the pressure of 6 and 8 Pa have high sp³ content and show typical diamond‐like character. However, the microstructures and bond configuration of the films deposited at 11, 15, and 20 Pa have high sp² content and favored fullerene‐like nanostructure. The hardness and sp² content were shown to reach their minimum values simultaneously at a deposition pressure of 8 Pa and then increased continuously. The film with fullerene‐like nanostructure obtained at 20 Pa displays a high Raman I_D/I_G ratio (~1.6), and low XPS C 1s binding energy (284.4 eV). The microstructural analysis indicates that the films are composed of a hard and locally dense fullerene‐like network, i.e. a predominantly sp²‐bonded material. The rigidity of the films is basically provided by a matrix of dispersed cross‐linked sp² sites. Copyright © 2012 John Wiley & Sons, Ltd.     

高效液相色谱-质谱法测定比格犬血浆中的艾普拉唑及其药代动力学

运用高效液相色谱-电喷雾质谱(HPLC-ESI-MS)技术,建立了快速、简单、灵敏的比格犬静脉滴注艾普拉唑钠盐后血药浓度的检测方法。血浆样品采用蛋白沉淀法,以丁螺环酮作为内标,色谱柱为Teknokroma Kromasil C18(100 mm×2.1 mm, 5 μm),流动相为水-甲醇-乙腈(69:8:23, v/v/v)(含0.1%的甲酸),流速0.2 mL/min,采用电喷雾(ESI)离子源以正离子方式检测。绘制血药浓度-时间曲线,并采用DAS 2.0计算药代动力学参数。方法学实验结果表明内源性杂质不干扰艾普拉唑和内标的测定,线性范围为5～10000 μg/L (r=0.994),最低定量限为5 μg/L,精密度和准确度均符合生物样品测定的要求。低、中、高3个浓度的绝对回收率在106%左右,基质效应小于142.0%,表明该方法适合比格犬血浆中艾普拉唑浓度的测定及药代动力学研究。比格犬静脉滴注艾普拉唑钠盐3个剂量(0.2 mg/kg、0.8 mg/kg和3.2 mg/kg)后的药-时曲线下面积(AUC(0~∞))分别为(2.4×104±3×103)、(8.8×104±1.6×104)和(5.4×105±8×104) μg/L•min,呈线性药物代谢动力学过程。     

HPLC analysis and pharmacokinetics of icariin in rats

As a prerequisite to the determination of pharmacokinetic parameters of icariin in rats, an HPLC method using UV detection was developed and validated. Icariin and the internal standard, quercetin, were extracted from plasma samples using ethyl acetate after acidification with 0.05 mol/L NaH2PO4 solution (pH 5.0). Chromatographic separation was achieved on an Agilent XDB Cls column (250 x 4.6 mm id, 5 microm) equipped with a Shim-pack GVP-ODS C18 guard column (10 x 4.6 mm id, 5 microm) using a mobile phase of ACN/water/acetic acid (31:69:0.4 v/v/v) at a flow rate of 1.0 mL/ min. Detection was at 277 nm. The calibration curve was linear from 0.05 to 100.0 microg/mL with 0.05 microg/mL as the lower LOQ (LLOQ) in plasma. The intra- and interday precisions in terms of RSD were lower than 5.7 and 7.8% in rat plasma, respectively. The accuracy in terms of relative error (RE) ranged from -1.6 to 3.2%. The extraction recoveries of icariin and quercetin were 87.6 and 80.1%, respectively. The main pharmacokinetic parameters for rats were determined after a single intravenous administration of 10 mg/kg icariin: t1/2, 0.562 +/- 0.200 h; AUC0-infinity, 8.73 +/- 2.23 microg x h/mL; CLToT, 20.10 +/- 5.80 L/kg x h; Vz, 1.037 +/- 0.631 L/kg; MRT0-infinity, 0.134 +/- 0.040 h; and Vss, 0.170 +/- 0.097 L/kg.     

Hydroxypropyl-beta-cyclodextrin enhanced fluorimetric method for the determination of melatonin and 5-methoxytryptamine

The effects of native cyclodextrins (alpha, beta or gamma), hydroxypropyl-beta-cyclodextrin, beta-cyclodextrin solubilized in urea, soluble starch and glucose in water solution on the fluorescence behaviour of melatonin (N-acetyl-5-methoxytryptamine) (M) and 5-methoxytryptamine [5-methoxy-3-(2-aminoethyl)indole] (5M) were determined. In addition, the effect of methanol and propanol with and without beta-cyclodextrin or hydroxypropyl-beta-cyclodextrin was assessed. From the fluorescence changes with pH, the values of the pKa for the ground (9.9 +/- 0.2) and the excited state (7.7 +/- 0.2) for 5M were determined. From the fluorescence changes with beta-cyclodextrin or hydroxypropyl-beta-cyclodextrin, the association constants of M, 5MH [5-methoxy-3-(2-ammoniumethyl)indole] and 5M with the two hosts were determined. The values with beta-cyclodextrin were KAssoc5MH = (1.4 +/- 0.4) x 10(2) mol-1 dm3, KAssoc5M = (1.6 +/- 0.1) x 10(2) mol-1 dm3 and KAssocM = (1.1 +/- 0.2) x 10(2) mol-1 dm3, and with hydroxypropyl-beta-cyclodextrin KAssoc5MH = (1.1 +/- 0.3) x 10(2) mol-1 dm3, KAssoc5M = (2.5 +/- 0.1) x 10(2) mol-1 dm3 and KAssocM = (1.51 +/- 0.07) x 10(2) mol-1 dm3. The ratios of the fluorescence quantum yields for the bound and free substrate (phi b/phi f) were in the range 1.15-1.48. The detection limits under the optimum conditions were 0.381 +/- 0.001 ng cm-3 for the complex 5MH-hydroxypropyl-beta-cyclodextrin in water and 0.290 +/- 0.001 ng cm-3 for the complex M-hydroxypropyl-beta-cyclodextrin in water with 5% of methanol. The recovery of melatonin from pharmaceutical preparations was 98-103% with an RSD of 2%. The recovery from rat pineals was also good. The method is direct, simple and accurate.     

On the photochemistry of IONO2: absorption cross section (240-370 nm) and photolysis product yields at 248 nm

The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. M?ssinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO) 相似文献   

Mechanical and optical properties of SiO<Subscript>2</Subscript> thin films deposited on glass

The optical and mechanical properties of amorphous SiO₂ films deposited on soda-lime silicate float glass by reactive RF magnetron sputtering at room temperature were investigated in dependence of the process pressure. The densities of the films are strongly influenced by the process pressure and vary between 2.38 and 1.91 g cm^?3 as the pressure changes from 0.27 to 1.33 Pa. The refractive indices of the films shift between 1.52 and 1.37, while the residual compressive stresses in the deposited films vary in the range from 440 to 1 MPa. Hardness and reduced elastic modulus values follow the same trend and decline with the increase of process pressure from 8.5 to 2.2 GPa and from 73.7 to 30.9 GPa, respectively. The abrasive wear resistance decreases with the density of the films.     

A transparent boron-nitrogen thin film formed by plasma CVD out of the discharge region

A transparent boron-nitrogen thin film of thickness 550 nm was successfully deposited out of the discharge region by rf plasma CVD. The deposition was performed with diborane (4.8 vol % in N₂) as the reactant gas and argon as the carrier gas by an inductively coupled reactor at a frequency of 13.56 MHz. The transparent films could be obtained at a low pressure of about 30 Pa, at a discharge power level of 30 W, and at room temperature without heating the substrate. The thin films obtained by rf plasma are compared with those obtained by microwave plasma. Both the refractive index and the deposition rate for the films deposited by microwave plasma are discussed according to the deposition conditions.