Thorium: Phase transformations and equation of state to 300 GPa

Abstract

Equation of state and phase transformations of thorium metal have been investigated to 300 GPa at 300 K in a diamond anvil cell using energy dispersive X-ray diffraction employing synchrotron source. Phase transformations in the 70–100 GPa range indicative of 5f-electron bonding are observed and thorium metal is isostructural with its 4f counterpart cerium at ultra high pressures. The measured static equation of state of thorium to 300GPa (volume fraction V/V _o = 0.40) at 300K is given. At high pressures, the sd to f electronic transfer has significant influence on the measured equation of state of thorium.     

Diamond Composites with TiC,SiC and Ti 3 SiC 2 Bonding Phase

The problems connected with producing diamond composites with 30 wt.% of bonding phase in form of: SiC, TiC, and Ti 3 SiC 2 are presented in the paper. Increasing the fraction of the bonding phase within the composite generally helps to reduce internal stresses. Composites were sintered at pressure 8.0 - 0.2 GPa and temperature of 2070 - 50 K using the Bridgman type high pressure apparatus. Interactions in the diamond-SiC, the diamond-TiC, and the diamond-Ti 3 SiC 2 systems were studied by means of transmission electron microscope (TEM) and X-ray diffraction. Density was measured pycnometrically. The wear resistance studies of these composites were carried out using pin - on disc type laboratory equipment. Hardness was measured with Vickers apparatus. Results of measurements of physical and mechanical properties are reported.     

压力、温度以及时间对金刚石烧结体性能的影响

 采用熔渗法研究了烧结压力、烧结温度以及烧结时间对金属添加剂金刚石烧结体性能的影响;在1 400 ℃、5.8 GPa、12 min的烧结条件下,烧结出磨耗比为285×10³、金刚石颗粒未出现异常长大的金刚石烧结体;分析了烧结方法对烧结效果的影响。     

Electrochemical properties of compacts of nano-and microdisperse diamond powders in aqueous electrolytes

The electrochemical behavior of compacts of micro-and nanodisperse diamond powders were studied by using model redox K₃[Fe(CN)₆]-K₄[Fe(CN)₆] and Ce(SO₄)₂-Ce₂(SO₄)₃ systems in aqueous electrolytes. The current-voltage curves for compacts of microdisperse diamonds and the kinetics of reactions on these compacts in a solution of the [Fe(CN)₆]^3-/4- system are similar to those obtained by using a metal electrode. For nanodisperse diamonds, the same reactions are essentially irreversible.     

Metastable carbon allotropes in picosecond-laser-modified diamond

In this paper, we report on the bulk modifications of type IIa single-crystal diamond with visible 10-ps pulses (at λ = 532 nm) and microstructural changes characterized by the appearance of several ‘unidentifiable’ vibrational modes in the frequency range of 1000–1400 cm^?1 in the Raman spectra of laser-modified diamond. It is found that the new Raman modes are strongly pronounced in the spectra of high-stress regions in immediate proximity to the bulk microstructures in the absence of the G mode at ~1580 cm^?1 characteristic of the sp² phase. The high internal stresses are determined from the splitting of the triply degenerate diamond Raman line. The revealed structure transformation is localized within a narrow bulk layer near the bulk microstructures formed, and the stress relaxation is found to result in disappearance of the detected vibrational modes in the spectra. It is suggested that the formation of bulk regions with a sp³ carbon structure consisting of Z-carbon and hexagonal diamond is responsible for the appearance of new Raman modes in the spectra of laser-modified diamond. These findings evidence that the stress-assisted formation of novel metastable carbon phases or defect structures occur in the course of bulk modification of diamond with ps-laser pulses. In addition, we report the results of simulations of internal stresses in the system ‘graphitized cylinder-in-diamond’ to show (1) the effect of the mechanical properties of laser-modified diamond on the resulting stresses and (2) formation of bulk microscopic regions with high stresses of >10 GPa, i.e., the conditions at which various sp³ carbon allotropes and defect structures become more stable than graphite.     

Effects of hydrogen and oxygen on the electrochemical corrosion and wear-corrosion behavior of diamond films deposited by hot filament chemical vapor deposition

A diamond film was deposited on silicon substrate using hot filament chemical vapor deposition (HFCVD), and H₂ and O₂ gases were added to the deposition process for comparison. This work evaluates how adding H₂ and O₂ affects the corrosion and wear-corrosion resistance characteristics of diamond films deposited on silicon substrate. The type of atomic bonding, structure, and surface morphologies of various diamond films were analyzed by Raman spectrometry, X-ray diffraction (XRD) and atomic force microscopy (AFM). Additionally, the mechanical characteristics of diamond films were studied using a precision nano-indentation test instrument. The corrosion and wear-corrosion resistance of diamond films were studied in 1 M H₂SO₄ + 1 M NaCl solution by electrochemical polarization. The experimental results show that the diamond film with added H₂ had a denser surface and a more obvious diamond phase with sp³ bonding than the as-deposited HFCVD diamond film, effectively increasing the hardness, improving the surface structure and thereby improving corrosion and wear-corrosion resistance properties. However, the diamond film with added O₂ had more sp² and fewer sp³ bonds than the as-deposited HFCVD diamond film, corresponding to reduced corrosion and wear-corrosion resistance.     

Investigation of properties of Cu containing DLC films produced by PECVD process

Copper containing diamond like carbon (Cu-DLC) thin films were deposited on various substrates at a base pressure of 1×10^?3 Torr using a hybrid system involving DC-sputtering and radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD) techniques. The compressive residual stresses of these films were found to be considerably lower, varying between 0.7 and 0.94 GPa and Cu incorporation in these films improve their conductivity significantly. Their structural properties were studied by Raman spectroscopy, atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques that clearly revealed the presence of Cu in the DLC structure. Raman analysis yields that Cu incorporation in DLC enhances the graphite-like sp² bonding. However, the sp² bonding was found to continuously reduce with the increasing C₂H₂ gas pressure, this may be due to reduction of Cu nanocrystal at the higher pressure. FTIR results inferred various bonding states of carbon with carbon, hydrogen and oxygen. In addition, hydrogen content and sp³ and sp² fractions in different Cu-DLC films were also estimated by FTIR spectra and were correlated with stress, electrical, optical and nano-mechanical properties of Cu-DLC films. The effect of indentation load (4–10 mN) on nano-mechanical properties of these films was also explored.     

Metal-diamond semiconductor interface and photodiode application

Carrier transport mechanism at p-diamond/metal interfaces are studied by analyzing dependencies of specific contact resistance (ρ_c) on measurement temperature and acceptor concentration (N_A). A variety of metals, such as Ti, Mo, Cr (carbide-forming metals), Pd, and Co (carbon-soluble metals), are deposited on boron-doped polycrystalline diamond layers, and the ρ_c values are measured by a transmission line method. Thermal annealing which produces metallurgical reactions between diamond and metal reduces Schottky barrier heights of the contact metals to a constant value. It is found that use of a metal compound which does not react with diamond at elevated temperatures is the key to develop the thermally stable Schottky contact material for p-diamond. Along this guideline, we test the suitability of tungsten carbide (WC) and hafnium nitride (HfN) as thermally stable Schottky contacts to develop a thermally stable, deep-ultraviolet (DUV) photodiode using a boron-doped homoepitaxial p-diamond epilayer. Thermal annealing at 500 °C improves the rectifying current-voltage characteristics of the photodiode, resulting in the excellent thermal stability. The discrimination ratio between DUV and visible light is measured to be as large as 10⁶ at a reverse bias voltage as small as 2 V, and it remains almost constant after annealing at 500 °C for 5 h. Metal carbide and nitride contacts for diamond are thus useful for developing a thermally stable diamond DUV photodetector.     

RAMAN AND INFRARED SPECTRA OF IODOFORM AT HIGH PRESSURES

ABSTRACT

Raman and infrared spectra are reported for iodoform samples in diamond anvil cells at ambient temperature and at pressures up to 5 GPa (Raman) and 10 GPa (infrared). The spectra appear to evolve smoothly and no evidence of any structural phase transitions is found. The dependence on pressure of 7 Raman and 13 infrared peak wavenumbers is presented. A large increase in intermolecular bonding strengths is confirmed, together with a moderate increase in intramolecular I-C-I bending forces. Color changes in the samples at high pressures are found to be mostly reversible, but long exposure to high fluxes of visible photons causes some molecular dissociation, with the release of iodine.     

Thermal conductive performance of deposited amorphous carbon materials by molecular dynamics simulation

A series of diamond-like carbon (DLC) films with different microstructure were prepared by depositing carbon atoms on diamond surface with incident energy ranging from 1 to 100 eV. The thermal conductivity of the deposited films and the Kapitza resistance between the film and the diamond substrate were investigated. Results show that the average density, the average fraction of sp³ bonding and the thermal conductivity of the DLC films increase first, reaching a maximum around 20–40 eV before decreasing, while the Kapitza resistance decreases gradually with increased deposition energy. The analysis suggests that the thermal resistance of the interface layer is in the order of 10^?10 m²K/W, which is not ignorable when measuring the thermal conductivity of the deposited film especially when the thickness of the DLC film is not large enough. The fraction of sp³ bonding in the DLC film decreases gradually normal to the diamond surface. However, the thermal conductivity of the film in normal direction is not affected obviously by this kind of structural variation but depends linearly on the average fraction of sp³ bonding in the entire film. The dependence of the thermal conductivity on the fraction of sp³ bonding was analysed by the phonon theory.     

掺杂CVD金刚石薄膜的应力分析

在不同实验条件下，用微波等离子体化学气相沉积(MPCVD)技术在Si基体上制备了S掺杂和B-S共掺杂CVD金刚石薄膜，利用X射线衍射仪和拉曼光谱仪研究掺杂对CVD金刚石薄膜的应力影响.研究结果发现，随着S掺杂浓度的增加，薄膜中sp²杂化碳含量和缺陷增多，CVD金刚石薄膜压应力增加；小尺寸的B原子与大尺寸的S原子共掺杂时，微量B的加入改变了CVD金刚石薄膜的应力状态，共掺杂形成B-S复合体进入金刚石晶体后降低金刚石晶体的晶格畸变程度，减少S原子在晶界上偏聚数量和晶体中非金刚石结构相含量，降低由于杂质、缺陷及sp²杂化碳含量产生的晶格畸变和薄膜压应力，提高晶格完整性. 关键词： 金刚石薄膜 掺杂 应力     

聚晶金刚石复合体超高压液相烧结理论研究

 在对前人有关聚晶金刚石超高压烧结机理的综合分析与评价的基础上,通过对金刚石与不同组分的钴熔体相互作用规律,及金刚石从钴熔体中的结晶热力学与动力学的理论研究,提出了石墨优先金刚石“溶解”和金刚石石墨化“溶解”的观点,阐明了钴熔体的性质对金刚石（石墨）的浸润扩散溶解过程,以及金刚石再结晶析出过程的影响,认为在金刚石-钴烧结系统中存在三种主要烧结机构：颗粒重排,溶解-析出和聚晶固架形成机构。不同温度条件下不同碳含量钴熔体在烧结过程中,对于促进金刚石表面石墨化,进一步引起颗粒重排,实现sp³结构碳原子在金刚石颗粒间的有效迁移传递以及D-D直接结合等方面起到了十分重要的作用。根据上述金刚石超高压液相烧结理论的基本观点,可较合理地解释聚晶金刚石复合体（PDC）在超高压烧结过程中观察到的一些基本现象和实验事实。     

Laser-assisted activation of dielectrics for electroless metal plating

2 O₃, SiC, diamond, ZrO₂, etc. are presented. The activation of the dielectric surface can be achieved in a wide range of laser wavelengths and is stable in time. This activation allows selective deposition of various metals (Cu, Ni, Pt, Pd, etc.) with lateral dimensions of several μm. The model of the activation process is discussed. This deals with the modification of the band gap of the dielectric, which involves the appearance of a non-zero density of electronic states in the vicinity of the potential of electroless metal reduction. These electronic states can arise either from the formation of point defects in the ablated surface (for example, F centers in Al₂O₃, CeO₂, or ZrO₂) or from the band bending of the dielectric caused by residual mechanical stresses left in the material after laser ablation (SiC or diamond). The data on the activation of dielectrics by mechanical indentation are qualitatively consistent with the model. Received: 5 January 1998/Accepted: 7 January 1998     

Ab initio modelling of boron and nitrogen in diamond nanowires

In this study an analysis is presented of the bonding and structural properties of dehydrogenated and hydrogenated doped cylindrical diamond nanowires calculated using the Vienna Ab Initio Simulation Package, employing density functional theory within the generalized-gradient approximation. The dopants studied here have been inserted substitutionally along the axis of an infinite one-dimensional diamond nanowire and include the single-electron acceptor boron and the single-electron donor nitrogen. The doped nanowires have then been re-relaxed, and properties compared with the undoped structures. The structural properties of relaxed nanowires considered here include an examination bonding via the electron charge density, with the aim of providing a better understanding of the effects of dopants on the stability of diamond nanostructures and nanodevices.     

On compressibility of osmium metal

On the basis of the high-pressure diamond anvil cell experiments on Os metal, Cynn et al. [Phys. Rev. Lett. 88, 135701-1 (2002)] have reported that this metal has lower compressibility than diamond. In the present work we have reanalysed the experimental data of Cynn et al. We find that the bulk moduli of Os and diamond are close to each other, implying that Os metal is as incompressible as diamond, but not more so. Our first principles total energy calculations using the full potential linearised augmented plane wave method on Os and diamond also suggest the same results.     

D-D结合型金刚石聚晶的高压合成研究

 为了探索功能金刚石聚晶的高压合成，使其具有优异的透红外和散热性能，我们采取了提高合成压力、温度和尽量减少结合剂的办法进行试验。首先探索如何使合成的金刚石聚晶具有D-D型结合，然后尽量减少结合剂，以合成出高密度的D-D型金刚石聚晶。为了尽量减少结合剂含量，不用粉末混合法，而是分别采用7~14 μm和63~80 μm粒度的金刚石为原料，与纯Ni或Ni₇₀Mn₂₅Co₅合金为基底积层组装，通过高温高压下触媒金属向金刚石晶粒间渗透进行烧结生长。在6.3 GPa的压力和1 440~1 650 ℃的不同温度下分别保持3~40 min。所得到的金刚石聚晶在触媒金属渗透得充分的区域形成了D-D结合型结构，而没有发现碳化物生成及金刚石表面石墨化等现象。     

Stress-induced phase transitions in diamond

A phase transformation in diamond into an intermediate carbon phase (ICP) was revealed in regions of maximal shear stress of diamond anvils. The transition was stimulated by additional stresses supplied to the compressed anvils with torque by a rotation of the anvil around the anvil's axis; maximal shear stress approached 55 GPa during the rotation. Creation of an ICP is considered as a mechanism of the stress-induced stability loss of the diamond structure. The characteristic Raman bands of ICP near 250, 500, 650–850 and 1050–1390 cm^?1 were observed in the failure regions.     

Raman scattering in the submicrometer diamond membrane formed by the lift-off technique

Spectral characteristics of spontaneous Raman scattering in the submicrometer diamond membrane grown by the hydrogen implantation method are studied in comparison with the single-crystal diamond matrix. A shift in the main line of diamond one-photon excitation (sp ³-hybridization) at a frequency of 1324 cm^?1 is revealed in the diamond membrane. This fact indicates multiple internal strains (residual compression strains) due to residual defects and is a concequence of the use of the hydrogen implantation method (hydrogen is implanted into diamond to form a sacrificial layer.     

Enhancement of the thermal properties of silver-diamond composites with chromium carbide coating

The present work reports the enhancement of the thermal properties in Ag/diamond matrix composites reinforced with chromium carbide coated diamond particles. The coated diamond particles were characterized by x-ray diffraction, x-ray photoelectron spectroscopy and Raman spectra. The composites were synthesized by spark plasma sintering. The chromium carbide coating on the diamond particles resulted in composites exhibiting improved wettability and strong interfacial bonding between the diamond particles and Ag matrix. The composites with coated diamonds showed a low coefficient of thermal expansion of 8.24 × 10^?6/K and a high thermal conductivity of 695 W/mK at 60 % particle volume fraction, which greatly outperformed the composites with uncoated diamonds at the same particle volume fraction. The obtained results are useful for synthesizing Ag/diamond composites with greatly improved thermal performance.     

Diamond-like amorphous carbon and nanocrystalline diamond obtained by detonation method

Abstract

The diamond-like amorphous carbon phase was obtained by means of detonation compression of mixtures of an explosive with soot or graphite. The pycnometric density of powders after compression and treatment in boiling acids achieved 3.42 g/cm³. The X-ray and TEM study showed that fine-grained crystalline and nanocrystalline diamond was also present in the samples in addition to the diamond-like amorphous phase.