钛基底的纳米金刚石掺混纳米碳管的场发射特性

在纳米金刚石场发射的基础上, 研究了纳米金刚石掺混纳米碳管的场发射特性。采用电泳沉积法形成了纳米金刚石与纳米碳管的复合涂层, 经热处理后制备出阴极样品, 然后进行微观表征, 再进行场发射特性测试与发光测试。结果表明, 与未掺混的纳米金刚石阴极样品相比, 复合涂层阴极样品的场发射开启电场明显减小, 场发射电流提高, 在较低的电场下阳极表面荧光粉就可以发光, 但发光不均匀, 出现了"边沿发光"的现象。分析了纳米金刚石掺混纳米碳管场发射性能提高的机理, 是由于纳米碳管掺入之后, 涂层的电子输运能力得到增强, 涂层中有效发射体的数目增加。最后, 解释了"边沿发光"现象的成因。     

超纳米金刚石薄膜结构相变的第一原理分子动力学研究

纳米金刚石薄膜的结构相变非常复杂,对稳定性和物理性质又尤为重要。本文用第一性原理分子动力学模拟研究了超纳米金刚石薄膜的结构相变和表面重构。研究发现,纳米金刚石的表面碳团簇通过断开（111）面的σ键,形成具有碳六元环结构的石墨碎片;内部原子sp3杂化向sp2杂化转化的发生是从（111）面上成对C原子向石墨相转化时形成π键的过程中获得了能量,驱动石墨的转变由表层向心部逐渐进行。转变过程中存在一种洋葱状富勒烯和金刚石结构共存的过渡相——Bucky-diamond,表面悬空键的消除和表层的富勒烯外壳最大限度地降低了表面能和系统总能量,Bucky-Diamond结构稳定存在。     

退火时间对硼掺杂纳米金刚石薄膜微结构和电化学性能的影响

采用高分辨透射电镜、紫外和可见光Raman光谱及循环伏安法研究了1000 ℃下退火不同时间的硼掺杂纳米金刚石薄膜的微结构和电化学性能. 结果表明,随退火时间的延长,薄膜中纳米金刚石晶粒尺寸逐渐减小.当退火时间为0.5 h时, 金刚石晶粒尺寸由未退火样品的约15 nm减小为约8 nm, 金刚石相含量增加;当退火时间为2.0 h时,金刚石晶粒减小为2—3 nm, 此时晶界增多,金刚石相含量减少;退火时间为2.5 h时纳米金刚石晶粒尺寸和金刚石相含量又略有上升.晶粒尺寸和金刚石相含量的变化表明薄膜在退火过程中发生了金刚石和非晶碳相的相互转变.可见光Raman光谱测试结果表明,不同退火时间下, G峰位置变化趋势与I_D/I_G值变化一致,说明薄膜内sp²碳团簇较大时, 非晶石墨相的有序化程度较高.退火0.5, 1.0, 1.5和2.0 h时, 电极表面进行准可逆电化学反应,而未退火和退火时间为2.5 h时电极表面进行不可逆电化学反应.退火有利于提高薄膜电极的传质效率, 退火0.5 h时薄膜电极的传质效率最高,催化氧化性能最好.较小的晶粒尺寸、 较高的金刚石相含量以及纳米金刚石晶粒的均匀分布有利于提高电极表面反应的可逆性和催化氧化性能.     

非简谐振动对纳米金刚石表面性质的影响

借助米-里纳德-金斯势研究了纳米金刚石的Debye温度、表面能、表面压强、晶格参量随原子数和形状的变化规律, 探讨了非简谐振动和形状对其表面性质的影响.结果表明: 1)纳米金刚石的Debye温度和表面能随原子数的增多而增大, 其中杆状的Debye温度和表面能要小于立方形的值; 2)纳米金刚石的表面压强和低温时的晶格参量相对变化量随原子数N 的增多而减小,其中杆状的值要比立方形的值要大; 3)原子数较少时,非简谐振动效应和形状对纳米晶的Debye温度、表面能、 表面压强、晶格参量的影响显著.     

MPCVD方法制备军用光学元件纳米金刚石膜

介绍了用MPCVD方法制备纳米金刚石膜的工艺。用MPCVD方法实验研究了在光学玻璃上镀纳米金刚石膜:膜层厚度为0 4551μm,粒度小于200nm,表面粗糙度小于29 5nm,最大透过率为80%;平均显微硬度为34 9GPa,平均体弹性模量为238 9GPa,均接近天然金刚石的力学性能。与衬底材料表面应力-2 78GPa相比,具有较好的抗压和耐磨效果。     

纳米GaP材料Ga填隙缺陷的EPR实验观察

利用电子顺磁共振(EPR)技术对纳米GaP粉体材料的本征点缺陷进行了研究，结果表明：由EPR信息的g因子值（2.0027±0.0004）可以确定纳米GaP粉体材料存在Ga自填隙（Ga_i）本征缺陷；纳米GaP粉体EPR信号超精细结构消失，以及谱线线宽（ΔH_PP）变窄等实验现象，可能是由纳米材料界面的无序性，以及缺陷原子和界面原子之间的电子交换造成的；在较低的测试温度范围内，升高温度引起纳米GaP材料发生晶界结构弛豫；当测试温度由100 K升高至423 K时，ΔH_PP值和自由基浓度皆逐渐降低.     

纳米金刚石的变温场发射

研究了温度变化对沉积在钛基底上的纳米金刚石的场发射特性的影响,发现纳米金刚石场发射电流随温度和电场的升高而增大,场发射特性偏离了传统的Fowler-Nordheim理论,场发射电流的稳定性基本没有变化.分析了场发射电流增大的机理,表明是由于纳米金刚石的尺度效应以及外电场下金刚石产生了大量的热载流子共同作用的结果.研究还表明基底钛在温度升高到一定程度后,在外加电场下会有较大的电流产生,对场发射造成较大的影响,表明基底钛具有一定的温度敏感性和电压敏感性. 关键词： 场发射 纳米金刚石 尺度效应 热载流子     

磷离子注入纳米金刚石薄膜的n型导电性能与微结构研究

系统研究了磷离子注入并在不同温度退火后的纳米金刚石薄膜的微结构和电学性能.研究表明,当退火温度达到800 ℃以上时,薄膜呈良好的n型电导.Raman光谱和电子顺磁共振谱的结果表明,薄膜中金刚石相含量越高和完整性越好,薄膜电阻率越低. 这说明纳米金刚石晶粒为薄膜提供了电导.1000 ℃退火后,薄膜晶界中的非晶石墨相有序度提高,碳悬键数量降低,薄膜电阻率升高.薄膜导电机理为磷离子注入的纳米金刚石晶粒提供了n型电导,非晶碳晶界为其电导提供了传输路径. 关键词： 纳米金刚石薄膜 n型 磷离子注入     

单晶硅纳米切削中C–C键断裂对金刚石刀具磨损的影响

本文基于分子动力学方法模拟金刚石刀具纳米切削单晶硅, 从刀具的弹塑性变形、C–C键断裂对碳原子结构的影响以及金刚石刀具的石墨化磨损等方面对金刚石刀具的磨损进行分析, 采用配位数法和6元环法表征刀具上的磨损碳原子. 模拟结果表明: 在纳米切削过程中, 金刚石刀具表层C–C键的断裂使其两端碳原子由sp³杂化转变为sp²杂化, 同时, 表面上的杂化结构发生变化的碳原子与其第一近邻的sp²杂化碳原子所构成的区域发生平整, 由金刚石的立体网状结构转变为石墨的平面结构, 导致金刚石刀具发生磨损; 刀具表面低配位数碳原子的重构使其近邻区域产生扭曲变形, C–C键键能随之减弱, 在高温和高剪切应力的作用下, 极易发生断裂; 在切削刃的棱边上, 由于表面碳原子的配位严重不足, 断开较少的C–C键就可以使表面6 元环中碳原子的配位数都小于4, 导致金刚石刀具发生石墨化磨损.     

纳米金刚石的变温场发射

研究了温度变化对沉积在钛基底上的纳米金刚石的场发射特性的影响,发现纳米金刚石场发射电流随温度和电场的升高而增大,场发射特性偏离了传统的Fowler-Nordheim理论,场发射电流的稳定性基本没有变化.分析了场发射电流增大的机理,表明是由于纳米金刚石的尺度效应以及外电场下金刚石产生了大量的热载流子共同作用的结果.研究还表明基底钛在温度升高到一定程度后,在外加电场下会有较大的电流产生,对场发射造成较大的影响,表明基底钛具有一定的温度敏感性和电压敏感性.     

Types of paramagnetic centers in Cu2+ complexes with model neuromelanins

Electron paramagnetic resonance (EPR) spectroscopy was used to examine free radical properties of model neuromelanins obtained by oxidative polymerization of noradrenaline, adrenaline and dopamine. We compared the lineshape of the experimental spectra, type and concentration of free radicals in the analyzed samples. The effect of different concentrations of Cu²⁺ on free radicals in melanins was studied. The total concentration of free radicals (about 10¹⁸ to 10¹⁹ spin/g) in the studied melanins increases as follows: adrenaline-melanin < dopamine-melanin < noradrenaline-melanin. EPR spectra of dopamine-melanin and adrenaline-melanin were a single EPR line (ΔB _pp, 0.50 and 0.55 mT, respectively). o-Semiquinone free radicals with the characteristicg-value of 2.0040 exist in these melanins. EPR spectra of noradrenaline-melanin were a superposition of two lines (ΔB _pp, 0.45 and 0.81 mT). o-Semiquinone free radicals were responsible for the narrower component. Nitrogen free radicals with ag-factor of 2.0030 were probably responsible for the broader component. Paramagnetic copper ions quenched the EPR signals of melanin free radicals in the studied samples. For melanin-Cu²⁺ complexes, broad EPR lines (ΔB _pp, 10–32 mT) of copper ions with ag-value of about 2.1 appeared. The influence of the microwave power on the EPR spectra of these complexes demonstrated the fast spin-lattice relaxation in the copper system in melanins.     

EPR of C60 thermal/photochemical reactions with polystyrene and polymethyl methacrylate

Thermal and photochemical free radical reaction products of C₆₀ with polymethyl methacrylate (PMMA) and polystyrene (PS) in orthodichlorobenzene solution were detected by EPR (electron paramagnetic resonance). Thermal radicals (<100°C) of C₆₀/PMMA and C₆₀/PS samples gave single line first-derivative EPR spectra withg=2.0029. Ultraviolet photolysis of a C₆₀/PMMA solid phase sample gave two radical species; whereas, photolysis of a C_60/PS solid phase sample gave only one free radical. EPR signals were also recorded for UV and thermal C₆₀ reaction with free radical initiator, azobis(isobutyronitrile).     

Roles of free radical on the formation of acetaldehyde in model wine solutions under different ultrasound parameters: A key bridge-link compound for red wine coloration during ageing

In order to explore the effects of ultrasound on the formation of acetaldehyde and its mechanism in model wine solutions, ultrasound conditions and free radicals were investigated by response surface methodology and electron paramagnetic resonance spectroscopy (EPR), respectively. The results indicate that ultrasound does induce the production of acetaldehyde with the maximum amount under the conditions of ultrasound power density 0.2 W/cm², 48 min and 32 °C. The hydroxyl radicals and the 1-hydroxyethyl free radicals are the main initiator and precursor for acetaldehyde, respectively. Furthermore, the stronger the 1-hydroxyethyl free radicals captured by EPR, the lower the formation of acetaldehyde. In addition, the content of Fe²⁺and ethanol also exerted a certain influence on the acetaldehyde formation. In conclusion, ultrasound does promote the production of acetaldehyde in the model wine solutions, which is beneficial for well understanding the mechanism of ultrasound in modifying the wine color and accelerating ageing.     

Time-resolved EPR study of electron spin polarization and spin exchange in mixed solutions of porphyrin stable free radicals

The time-resolved electron paramagnetic resonance (EPR) spectra are studied in the temperature range of 110–300 K for two mixed solutions of porphyrins, ZnTPP and H₂TPP, in toluene and the stable free radical 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO). The EPR spectra and their kinetic behavior were studied for concentrations of TEMPO varied in the interval from 0.51 to 7.68 mM, while the porphyrin concentration was fixed as 1 mM. The EPR spectra of triplet-state porphyrins and free radicals manifest the chemically induced spin polarization. For the relatively short-lived radical-triplet pairs, with the perturbation theory up to the fourth order, the theoretical expressions are obtained for the triplet and radical spin polarization induced by the enhanced intersystem crossing (ISC) due to the interaction of excited singlet-state porphyrins with free radicals and by the triplet quenching by free radicals. The time-dependent EPR spectra of the triplets are simulated taking into account the spin-lattice relaxation. It is shown that the variation of the triplet EPR spectra shape, when the time of observation increases, arises from the spin-lattice relaxation kinetics. The kinetic behavior of the TEMPO EPR spectrum was simulated on the basis of the kinetic scheme suggested earlier in the literature. The triplet spin-lattice relaxation time, the rate of the ISC and the lifetime of the excited singlet state were estimated by fitting the kinetic curves for the triplet EPR spectra intensity. For the mixed porphyrin-TEMPO solutions, a possible set of the rate constants of important bimolecular processes were determined. For this set of parameters, it turns out that the spin polarization transfer has a smaller rate constant than the rate constant of the diffusion collisions of the triplet and radical. It appears that the rate constant of the ISC catalyzed by radicals is relatively high in the solutions close to the melting point of the solvent and in the soft-glassy state. In the triplet porphyrins the initial spin polarization induced by the spin-selective ISC was found to exceed the equilibrium spin polarization by up to two orders of magnitude.     

Application of EPR spectroscopy to examination of gentamicin and kanamycin binding to DOPA-melanin

Electron paramagnetic resonance (EPR) spectroscopy was applied to measure the influence of two aminoglycoside antibiotics: gentamicin and kanamycin on free radical propertis of DOPA-melanin. DOPA-melanin was formed by oxidative polymerization of 3,4-dihydroxyphenylalanine. Different concentrations of gentamicin and kanamycin (from 1·10⁻⁴ to 1·10⁻² M) were used. o-Semiquinone free radicals with ag factor of 2.0043 were found in all studied melanin samples. Their concentrations in the DOPA-melanin-drug complexes were higher than in DOPA-melanin, and increased with the increase of gentamicin and kanamycin concentration. A single EPR line of the analyzed samples (ΔB _pp, 0.48-0.52 mT) indicates that aminoglycoside antibiotics do not create a new type of free radicals in DOPA-melanin. Microwave saturation behavior of the experimental lines indicates the homogeneous broadening of resonance absorption curves for DOPA-melanin and its complexes with aminoglycosides. The EPR lines saturate at low microwave powers. Slow spin-lattice relaxation processes were characteristic for all studied melanin samples.     

A study of the temperature dependence of the rate constant for the reaction of O<Subscript>2</Subscript> with surface alkoxy radicals

A method for studying the reactions of surface alkoxy radicals with O₂ at temperatures of 230 to 300 K is described. Alkoxy radicals were generated directly in the cavity of an EPR spectrometer. Surface organic radicals, prepared from paraffin wax ((CH₃)₂(CH₂) _n , n = 16–20), were applied to Aerosil particles from a solution in heptane. The Aerosil sample was placed in the cavity of the EPR spectrometer in a cylindrical cup with a central hole for pumping out gases and exposed to H atoms. In this way, it is possible observe a steady increase in the EPR signal from the surface radicals. To measure the rate constant at tropospheric temperatures, the reaction tube was placed in a Teflon jacket, through which cool nitrogen vapor was pumped. The temperature in the reactor was varied from 230 to 300 K. The recorded EPR spectra belong to the (RO) _s radical. After obtaining a stable EPR signal from the surface radicals, treatment with H atoms was stopped, additional flow of O₂ was introduced ([O₂] = 10¹⁴–10¹⁶ cm⁻³), and the reaction of O₂ with the surface organic radicals was studied by monitoring the EPR signal decay. The temperature dependence of the rate constant for the (RO) _s + O₂ → HO₂ + ketone was obtained within T = 230–300 K. The extrapolation of the data to real tropospheric conditions ([O₂] = 10¹⁸ cm⁻³) was performed.     

Heterogeneous reactions of H and O<Subscript>2</Subscript> with solid alkanes

The paper describes a new source of surface organic radicals whose special feature is a low rate of the initiation of alkyl radicals in reactions of H atoms with the surface of alkanes. A special reactor design was used to accumulate radicals at room temperature and observe alkoxyl radicals RO by the EPR method. For this purpose, alkanes were deposited on aerosil and placed into an EPR cavity. Thanks to the large area of aerosil loads (～10³ cm²), we were able to obtain a stable signal corresponding to a ～10¹⁷ total amount of alkoxyl radicals (the degree of surface coverage ～0.1%). When O₂ was introduced into the reactor in concentrations of 10¹⁵–10¹⁶ cm^?3, a sharp decrease in the signal from surface organic radicals was observed. The process was described as the first-order (RO) _s + O₂ → HO₂ + ketone reaction with a 1.7 × 10^?17 cm³ s^?1 rate constant.     

EPR investigations of structure of humic acids from compost, soil, peat and soft brown coal upon oxidation and metal uptake

Free radical concentration and theirg-values in humic acids (HA) isolated from various sources were studied by quantitative EPR technique. EPR data for HA formed during composting and natural humification processes occurring in soil, peat and brown coal are given. In more detail the EPR data were analyzed for brown coal HA under carbonization, air oxidation (150°C) as well as metal uptake (Ca(II), Zn(II), Cd(II), Hg(II), Co(II), Ni(II) and Cu(II)) and NO₂ reaction. Two groups of metal complexes were distinguished on the basis of their interaction with free radicals in HA. Ca(II), Zn(II), Cd(II) and Hg(II) ions increase free radical concentration, while Co(II), Ni(II) and Cu(II) ions quench the radicals compared to the raw HA. This phenomenon can be explained either by the strong interaction of the metal ions with active centres responsible for the quinone-hydroquinone-semiquinone equilibria, and/or by the antiferromagnetic interaction between radical spins and metal d orbitals. Gaseous ammonia was found to be a very useful base easily penetrating the solid matrix of HA and strongly influencing the equilibria. β-Diketone groups present in HA react with NO₂ yielding iminoxy radicals. In the HA-metal complexes these structural units are engaged in metal coordination which lowers effectiveness of the iminoxyl synthesis.     

Free radical scavenging activities of white and red wines: An EPR spin trapping study

Free radical scavenging activities of wine samples were investigated by means of electron paramagnetic resonance (EPR) spin trapping. 1,1-Diphenyl-2-picrylhydrazyl served as a source of free radicals, OH radicals were produced by the Fenton system, and in situ thermally generated SO₄⁻ radicals from K₂S₂O₈ and carbon-centered radicals from azo-compounds were also used. 5,5-Dimethylpyrroline-N-oxide (DMPO) was used as a spin trapping agent. Three white and four red wine samples from the Slovak wine regions, along with 12% (v/v) aqueous ethanol solution as a reference sample, were compared. In general, the lowest scavenger activity was found in the reference sample, a higher one in the white, and a considerably higher one in the red wines, except when the Fenton system was used as the radical source. Here, unexpectedly, unlike in the other radical sources, the wine samples increased the yield of DMPO-adducts by about 5 times, compared to the reference sample. This is probably due to an additional activation of the Fenton system by wine components. Higher concentrations of Mn²⁺ ions as determined by EPR spectroscopy corresponded to an increased scavenging activity of wines.     

EPR Studies of DOPA–Melanin Complexes with Fe(III)

Paramagnetic centers in 3,4-dihydroxyphenylalanine–melanin and its complexes with Fe(III) were examined by electron paramagnetic resonance (EPR) spectroscopy. Paramagnetic centers of melanin play an important role in detoxification of environment and they reveal high activity in binding of metal ions. Two different signals were observed in EPR spectra: lines of o-semiquinone free radicals and lines of paramagnetic Fe(III). Amplitudes of EPR lines of both free radicals and iron ions decrease with increasing Fe(III) content in melanin–metal ion complexes. Free radical concentrations in the melanin samples, g-factors, amplitudes and line widths of EPR spectra were determined. It was stated that fast spin–lattice relaxation processes exist in both free radical system and paramagnetic iron ions in melanin complexes.