o-C_8碳:新的超硬碳同素异形体（英文）

通过粒子群优化算法和密度泛函计算,证明了空间群为PMM A的正交晶系的碳同素异形体o-C_8是稳定的超硬相.声子谱计算表明,o-C_8碳相是动力学稳定的;体积压缩计算表明,它是体模量为298.6 GPa的高度不可压缩材料.o-C_8相是一种新型的密度为2.993 g/cm~3、维氏硬度为67.0 GPa的低密度超硬材料.     

透明的碳同素异形体

大多数人都知道碳的同素异形体不只一种,其中最常见的是金刚石和石墨,另外还有富勒烯、碳纳米管以及今年荣获诺贝尔奖的石墨烯。2003 年又发现了一种介于石墨和金刚石之间的体心四方结构（body-centred tetragonal,bct）同素异形体（如图）。首次对其研究的是筑波、东京和明尼苏达大学的梅本耕一郎（Koichiro Umemoto）和同仁。南开大学的周向峰和同事则做了进一步研究,虽然他们的工作仍停留在理论阶段,但是却解释了石墨压缩形成透明碳同位素异形体的实验现象。这种材料的硬度比金刚石更高,它在金刚石砧上按压后留下了印痕。透明的体心四方碳不仅只需很少的能量就能形成,其剪切强度甚至比金刚石还高出17%。如果这一结论能得以证实,也就意味着能在常温下制造出比金刚石更强的材料。     

PLD方法制备的超硬非晶碳薄膜研究

 用脉冲激光沉积在不同条件下制备非晶碳超硬薄膜,研究了非晶碳超硬薄膜的表面形貌、结构、应力、硬度以及能谱等。原子力显微镜和扫描电镜图像显示,薄膜表面平整、致密且光滑,均方根粗糙度最大为0.877 nm。在高激光重复频率、高激光通量条件下,薄膜有很大的应力,致使膜层褶皱甚至破裂,小角X射线衍射表明薄膜为非晶态且最大残余应力达30 GPa以上,但300 ℃温度的原位退火可以有效降低残余应力;纳米压痕测试表明薄膜硬度大于20 GPa,弹性模量大于200 GPa;X射线光电子能谱表明薄膜中sp3的含量在39%~53%之间变化,并且与激光通量成正比。     

基片偏压对MCECR溅射硬碳膜特性的影响

采用封闭式电子回旋共振(MCECR)氩等离子体溅射碳靶的方法在硅片上沉积了高质量的硬碳膜, 膜层厚度约40 nm. 使用X射线光电子能谱仪(XPS)和高分辨率透射电子显微镜(HRTEM)分析了碳膜结构,并用POD摩擦磨损仪测试了碳膜的摩擦磨损特性,用纳米压入仪测试了碳膜的纳米硬度.详细研究了基片偏压对碳膜的结构、摩擦磨损特性以及纳米硬度的影响,得到了最佳基片偏压.     

Hf8C12金属碳多面体电子结构的从头计算研究

用赝势从头计算方法研究Hf₈C₁₂多面体．先对T和Td分子构型作几何优化，发现Td对称构型比T构型稳定．利用非限制的Hartre Fock方法及自然键轨道分析研究Td构型的Hf₈C₁₂基团，结果表明：Hf₈C₁₂存在三种自旋不同的基态，这种基态的多样性与成键机制、电子组态和电子能谱分布密切相关．其中S=0时，Hf₈C₁₂主要是由外四面体Hf原子与类乙烯C₂单元形成极性共价键构成．S=1时，6个类乙炔C₂单元吸附在Hf₈金属框架．S=2时，部分C₂中的ｐπ键断裂与Hf原子形成ｄ←ｐπ键．进一步分析发现，Td对称性的结构模型为(Hf₈)^+4.5(C^-0.75₂)₆，在高自旋态下具有铁磁性，电子能级分布及其能隙随自旋态而变化． 关键词：     

使用发射光谱对H2稀释情况下的感应耦合H2/C4F8等离子体中碳氟基团的研究

在射频输入功率为400W，气压为0.8Pa的条件下，使用光强标定的发射光谱方法研究了感应耦合H₂/C₄F₈等离子体中CF, CF₂, H和F基团的相对密度随流量比R=H₂/(H₂+C₄F₈)的变化情况，而HF基团相对密度的变化由四级质谱仪探测得到。结果表明等离子体活性先随着R的增加而升高，然后随着R的进一步增加而下降。在流量比从0逐渐上升到0.625的过程中，CF和CF₂基团的相对密度不断降低。实验中测得的CF基团的相对密度[CF]与理论计算得到的[CF]有很好的一致性说明了电子与CF2基团的碰撞反应是CF基团产生的主要原因。文中还讨论了HF基团。     

C3N4薄膜的结构与性能研究

用射频等离子体增强化学汽相沉积技术合成C₃N₄薄膜，并采用强迫晶化技术，经透射电子衍射观测，薄膜具有多晶结构．用X射线光电子能谱测试了C，N原子结合能及含氮量．傅里叶变换红外光谱曲线表明薄膜中不含石墨相．测得薄膜的维氏硬度为29.2—50.0GPa 关键词：     

C2和C2+,C2-的电子结构与势形共振

本文在独立电子近似的基础上,根据多重散射自洽场理论方法,计算了C₂和C₂⁺,C₂^-分子(离子)的电子结构,阐明了势形共振能量和上述分子(离子)电子数的关系,结果表明,随着电子数的减少,C原子2s-2p轨道杂化减弱,势形共振的能量将降低(如降低到阈值下,则势形共振消失)。 关键词：     

C60分子电子激发态结构的理论研究

C₆₀分子有较丰富的分子键轨道,同时C₆₀分子离子是稳定存在的,因此预期C₆₀分子的里德伯轨道也是稳定存在的。本文在独立电子近似的基础上,应用多重散射自洽场方法,从理论上统一自洽地探讨了C₆₀分子的分子键轨道和分子里德伯轨道的能级结构。这些轨道能级结构在独立电子近似的层次上模拟了C₆₀分子的电子结构。所得结果和已有的理论和实验结果进行了比较和分析,说明本文结果是自洽合理的,并和已有的实验值符合良好 关键词：     

控制成核生长大尺寸C60，C70单晶

通过改进双温区双温度梯度方法，成功地控制成核密度，分别生长出线度可达6mm和5mm的大尺寸C₆₀，C₇₀单晶，并对其表面形貌和晶体结构进行了研究. 关键词：     

Theoretical study on UH4, UH8 and UH10 at high pressure

Stable structures of uranium hydrides at 0–550 GPa were studied using genetic algorithm (GA) combined with density functional theory calculations. We investigated two stoichiometries of U–H system, UH₄ and UH₁₀ at high pressure, and properties of UH₄, UH₈ and UH₁₀. The study found that UH₈ is the most stable phase at 100–550 GPa, UH₄ is a stable phase at 100–550 GPa, and UH₁₀ could become stable over 450 GPa. For UH₁₀, the most phase is $Fm\stackrel{￣}{3}m$, which was found to be a superconductor with the transition temperature $T_c=51,21,12,10$ and 15 K at 100, 200, 300, 400 and 550 GPa, respectively.     

Computational Prediction of a Novel Superhard SP~3 Trigonal Carbon Allotrope with Bandgap Larger than Diamond

Searching for new carbon allotropes with superior properties has been a longstanding interest in material sciences and condensed matter physics.Here we identify a novel superhard carbon phase with an 18-atom trigonal unit cell in a full-sp~3 bonding network,termed tri-C_(18) carbon,by first-principles calculations.Its structural stability has been verified by total energy,phonon spectra,elastic constants,and molecular dynamics simulations.Furthermore,tri-C_(18) carbon has a high bulk modulus of 400 GPa and Vickers hardness of 79.0 GPa,comparable to those of diamond.Meanwhile,the simulated x-ray diffraction pattern of tri-C_(18) carbon matches well with the previously unexplained diffraction peaks found in chimney soot,indicating the possible presence of tri-C_(18)carbon.Remarkably,electronic band structure calculations reveal that tri-C_(18) carbon has a wide indirect bandgap of 6.32 eV,larger than that of cubic diamond,indicating its great potential in electronic or optoelectronic devices working in the deep ultraviolet region.     

Oxidation of H2/CO2 mixtures and effect of hydrogen initial concentration on the combustion of CH4 and CH4/CO2 mixtures: Experiments and modeling

An experimental investigation of the oxidation of hydrogen diluted by nitrogen in presence of CO₂ was performed in a fused silica jet-stirred reactor (JSR) over the temperature range 800-1050 K, from fuel-lean to fuel-rich conditions and at atmospheric pressure. The mean residence time was kept constant in the experiments: 120 ms at 1 atm and 250 ms at 10 atm. The effect of variable initial concentrations of hydrogen on the combustion of methane and methane/carbon dioxide mixtures diluted by nitrogen was also experimentally studied. Concentration profiles for O₂, H₂, H₂O, CO, CO₂, CH₂O, CH₄, C₂H₆, C₂H₄, and C₂H₂ were measured by sonic probe sampling followed by chemical analyses (FT-IR, gas chromatography). A detailed chemical kinetic modeling of the present experiments and of the literature data (flame speed and ignition delays) was performed using a recently proposed kinetic scheme showing good agreement between the data and this modeling, and providing further validation of the kinetic model (128 species and 924 reversible reactions). Sensitivity and reaction paths analyses were used to delineate the important reactions influencing the kinetic of oxidation of the fuels in absence and in presence of additives (CO₂ and H₂). The kinetic reaction scheme proposed helps understanding the inhibiting effect of CO₂ on the oxidation of hydrogen and methane and should be useful for gas turbine modeling.     

Stability of silver clusters in mordenites with different SiO2/Al2O3 molar ratio

The stability and decay of silver clusters characterized by absorption bands 320 and 285 nm incorporated in mordenites with different SiO₂/Al₂O₃ molar ratios were studied under ambient conditions. Significantly different rates of disappearance of these two bands were the basis for assigning them to different silver species. Oxidation converts the clusters peaking at 320 and 285 nm into other silver clusters characterized by absorption bands at 310 and 240 nm, respectively. The oxidation of silver clusters peaking at 285 nm is significantly faster than that at 320 nm. The stability of both original clusters decreases with acid site strength that, in its turn, depends on Si0₂/Al₂O₃ molar ratio. The minimum lifetime of clusters peaking at 320 and 285 nm equal to ca. 40 and 20 days, respectively, was observed for mordenite characterized by the strongest acid sites. For mordenites possessing weaker acid sites, the lifetime of these clusters is found to be more than 50 months. The oxidation of silver clusters is reversible, and re-reduced silver clusters were revealed to possess the same electron structure as original ones.     

Generalised coexistence of a low work function and a stable surface: CaAl4 and BaAuIn3

Cathodes are used in many devices ranging from microwave ovens to organic light-emitting diodes (OLEDs). Crucial materials properties are a low work function (Φ) and a (relatively) stable surface. The relation between the two was not clear for more-complex metals. Our previous paper [M.A. Uijttewaal, G.A. de Wijs, R.A. de Groot, R. Coehoorn, V. van Elsbergen, C.H.L. Weijtens, Chem. Mater. 17 (2005) 3879] predicted, on the basis of results on BaAl₄, that stable low-work-function surfaces are more general for intermetallic compounds with polar surfaces. This paper strengthens the prediction by first-principles calculations on various surfaces of CaAl₄ and BaAuIn₃.     

Optical properties of TiO2 anatase - Carbon nanotubes composites studied by cathodoluminescence spectroscopy

Luminescence spectra obtained by electron bombardment (cathodoluminescence, CL) on TiO₂ (anatase)/carbon nanotubes (CNT) composite, show only one visible band at 498 nm, while the spectra taken from pure anatase samples show two bands at 498 and 545 nm. We demonstrate that the visible luminescence bands are originated by TiO₂ surface defects due to oxygen vacancies, and that this luminescence signal is independent of TiO₂ mineral form (anatase or rutile). Moreover we obtain that the 545 nm band quenching in TiO₂/CNT composites is caused by empty oxygen vacancies (OV) related to oxygen given from oxygen-rich pristine powder of carbon nanotubes. Our conclusions are also supported by X-ray photoelectron spectroscopy (XPS), SEM analysis and energy dispersed X-ray measurements (EDX). Furthermore we can confirm that the NIR TiO₂ luminescence emission is linked only to the presence of Ti rutile form as described in several works in literature.     

Mechanical properties and hardness of new carbon-rich superhard C11N4 from first-principles investigations

The structural, mechanical properties and hardness of the new carbon-rich material C₁₁N₄ are studied by first-principles total energy calculations based on the density-functional theory. We use the empirical equations of state (EOS) to investigate the lattice properties and bulk modulus. It is found that the calculated lattice constants and bulk modulus are in good agreement with previous calculations. And the full set elastic constants are calculated using the stress-strain method. The Voigt-Reuss-Hill approximation is used to evaluate the mechanical moduli. The elastic constants show that the two phases of C₁₁N₄ are mechanically stable. The tetragonal-C₁₁N₄ (α-C₁₁N₄) exhibits larger mechanical moduli than the orthorhombic-C₁₁N₄ (β-C₁₁N₄). The mechanical anisotropy is calculated of several different anisotropic indexes and factors, such as universal anisotropic index (A^U), the percent anisotropy (A_G and A_B) and shear anisotropic factors (A₁, A₂ and A₃). Furthermore, the hardness of α-C₁₁N₄ and β-C₁₁N₄ are evaluated according to the intrinsic hardness calculation theory. α-C₁₁N₄ is predicted to be a superhard material with the Vickers hardness of 67.17 GPa, which is slightly higher than that of the cubic boron nitride. And the β-C₁₁N₄ is also a superhard material with the calculated Vickers hardness of 45.63 GPa. C₁₁N₄ can be considered as candidate superhard compounds.     

Mechanical and magnetic properties of ZnO/Fe2O3 ceramic varistors

Mechanical and magnetic properties of the ZnO/Fe₂O₃ ceramic varistors have been examined by using mechanical analyzer, digital microhardness tester and vibrating sample magnetometer. The initial stress–strain behavior is found to be linear (elastic) then becomes nonlinear (plastic deformation) without reaching the failure limit up to the maximum available stress (0.07 MPa). The compressive elastic modulus varies between 0.2 and 0.8 MPa with Fe addition up to 0.50. Furthermore, an approximately monotonically linear decrease in VHN with increasing Fe content up to 50% has been observed for all applied loads, which closely resembles the behavior of the true hardness and the surface energy. The magnetic measurements revealed an antiferromagnetic to paramagnetic to transition for all Fe doped samples. The Fe free sample showed paramagnetic behavior down to 2 K. The Neel temperature moderately increased from 18 K at 0.05% Fe to 25 K at 0.5% Fe. The magnetization (M) versus applied magnetic field (H) did not reach saturation for all samples up to 9 Tesla. The saturated magnetization (per Fe contents) is low and found to decreases linearly at a rate of (−35 emu/g-Fe) in a clear manifestation of the strengthening of the antiferromagnetic exchange interaction with increasing Fe contents.     

Mathematical modeling of TE CO2 laser with SF6 as a saturable absorber

A mathematical model describing the dynamic emission of a single mode TE CO₂ laser with saturable absorber has been adapted. A six-temperature model has been used to describe the amplifying medium, while a four-coupled energy level is used to describe the selective absorbing medium. The suggested mathematical model allows the investigation of the effects of the intracavity absorber on the mode characteristics of the TE CO₂ laser and, moreover, the study of the effect of the laser input parameters on the output laser pulse. The model simulates the passive Q-switch in both low- and high-pressure cases in the absorbing medium.

In addition, numerical solutions of a non-linear rate equation system of the suggested model are quantitatively discussed. The solutions describe the photon number density, the population inversion and the energy transfer processes of amplifying and absorbing media.