高温高压下碳的状态方程及相变理论研究

 研究了高温高压下三相碳（石墨、金刚石、液相碳）的状态方程，包括高压下石墨到金刚石的固-固相变以及高温下石墨和金刚石的熔解曲线。计算所得到的金刚石熔解曲线具有正的斜率，石墨-金刚石-液相三相点为4 400 K，14 GPa左右。     

Melting of carbon heated by focused laser radiation in air at atmospheric pressure and temperature below 4000 K

The melting of carbon at a pressure of about 1 atm is observed. The escape of liquid carbon from the heating region and its spread over the sample surface are observed in the experiments. The structural changes in graphite occurring in the melting region are determined from scanning tunneling microscope (STM) images obtained by means of an atomic force microscope and from Raman spectra. The STM images exhibit significant rearrangement of the structure of the graphite surface in the region of the escape of liquid carbon. The Raman spectra show that the graphite ordering degree increases significantly.     

Optical and Electrical Properties Evolution of Diamond-Like Carbon Thin Films with Deposition Temperature

Optical and electrical properties of diamond-like carbon （DLC） films deposited by pulsed laser ablation of graphite target at different substrate temperatures are reported. By varying the deposition temperature from 400 to 25℃, the film optical transparency and electrical resistivity increase severely. Most importantly, the transparency and resistivity properties of the DLC films can be tailored to approaching diamond by adjusting the deposition temperature, which is critical to many applications. DLC films deposited at low temperatures show excellent optical transmittance and high resistivity. Over the same temperature regime an increase of the spa bonded C content is observed using visible Raman spectroscopy, which is responsible for the enhanced transparency and resistivity properties.     

Critical role of laser wavelength on carbon films grown by PLD of graphite

The structure of thin films deposited by pulsed laser ablation (PLD) is strongly dependent on experimental conditions, like laser wavelength and fluence, substrate temperature and pressure. Depending on these parameters we obtained various kinds of carbon materials varying from dense, mainly tetrahedral amorphous carbon (ta-C), to less compact vertically oriented graphene nano-particles. Thin carbon films were grown by PLD on n-Si 〈100〉 substrates, at temperatures ranging from RT to 800°C, from a rotating graphite target operating in vacuum. The laser ablation of the graphite target was performed by a UV pulsed ArF excimer laser (λ=193 nm) and a pulsed Nd:YAG laser, operating in the near IR (λ=1064 nm). The film structure and texturing, characterised by X-ray diffraction analysis, performed at grazing incidence (GI-XRD), and the film density, evaluated by X-ray reflectivity measurements, are strongly affected both by laser wavelength and fluence and by substrate temperature. Micro-Raman and GI-XRD analysis established the progressive formation of aromatic clusters and cluster condensation into vertically oriented nano-sized graphene structures as a direct function of increasing laser wavelength and deposition temperature. The film density, negatively affected by substrate temperature and laser wavelength and fluence, in turn, results in a porous bulk configuration and a high macroscopic surface roughness as shown by SEM characterisation. These structural property modifications induce a relevant variation also on the emission properties of carbon nano-structures, as evidenced by field emission measurements. This work is dedicated to our friend Giorgio who passed away 20th August.     

TiC-MgO composite: an X-ray transparent and machinable heating element in a multi-anvil high pressure apparatus

ABSTRACT

TiC-MgO composite was developed as a heating element for X-ray study in the multi-anvil high pressure apparatus. We synthesized TiC-MgO blocks (50–70 wt.% of TiC) by compression in a cold isostatic press followed by baking in a gas flow furnace. Heaters of tubular shape were manufactured from the synthesized blocks either by lathe or numerically controlled milling machine. The so-produced heating elements have been proved to generate temperatures up to 2250?K at 10?GPa, condition where classical graphite heaters are not suitable anymore due to graphite-diamond transition. These new heaters have been successfully used for in situ X-ray radiography and diffraction measurements on liquid Fe alloys, exploiting excellent X-ray transparency.     

Pressure and Time Dependences of the Supercooled Liquid-to-Liquid Transition in Sulfur

Thermal behavior of bulk amorphous sulfur is investigated by in situ temperature measurements at high pressures of 0.9,1.4 and 2.1 GPa,and under different heating rates of 8,10 and 12K/min at 0.9 GPa.The results show that the onset temperature of the transition from the supercooled liquid to the liquid state for sulfur increases with the pressure and the heating rate.It is deduced that the transition does not follow the Clapeyron equation,indicating considerable coupling of the molecular structure change in the transition.Along with the data at ambient pressure and high pressure,we present a dynamic diagram to demonstrate the relationship between the amorphous solid,supercooled liquid,liquid,and crystal phases of sulfur,and suggest an experimental approach to establish pressure-temperature-time transition diagrams for supercooled liquid and liquid.     

铜丝水中电爆炸能量沉积特性

对s脉冲电压作用下铜丝水中电爆炸的能量沉积过程进行了实验研究,利用自积分Rogowski线圈和电阻分压器分别测量铜丝电爆炸时的电流和电压。利用测量电压波形确定了熔融起始、熔融结束、汽化起始和击穿时刻点,将铜丝电爆炸划分成熔融、液态和汽化3个阶段。通过数学方法计算了3个阶段和击穿前的沉积总能量。通过实验和计算,分析了电路参数,包括放电电压和回路电感,以及铜丝特性,包括铜丝长度和直径,对铜丝电爆炸过程中3个阶段和击穿前沉积总能量的影响。结果表明:在s脉冲电压作用下,放电电压、回路电感、铜丝长度和直径对熔融阶段能量沉积影响较小,但对液态和汽化阶段能量沉积影响较大,通过调节电路参数提高电流上升速率,可以显著提高汽化和击穿前的沉积能量。     

Characterization of a 10-MHz quadrant APD for measuring frequency oscillations and tip displacements of microcantilevers

The room-temperature response of a 10-MHz quadrant avalanche photodiode (APD) is investigated for detection of high frequency oscillations and tip displacements of fabricated microcantilevers. Currently, no quadrant detectors with a response bandwidth in the megahertz range are available, and oscillations on the order of a few microseconds cannot be resolved. A comparison is made between optical and opto-mechanical measurements to characterize this detector by investigating the frequency response and signal-to-noise (SNR) of pulsed laser signals up to 10?MHz and reflected laser signals from freely vibrating microcantilevers up to 1.64?MHz. The power level of the minimum detectable signal incident on the APD is found to be 28.2?±?5.0?nW for optical measurements and 1.0???W?±?5.0?nW for opto-mechanical measurements.     

Laser Pump-Probe Fiber-Optic Technique for Characterization of Near-Surface Layers of Solids: Development and Application Prospects for Studying Semiconductors and Weyl Semimetals

A fiber-optic setup incorporating the pump-probe thermoreflectance (TR) technique with Fabry–Perot (FP) interferometer is presented. It includes both heat pump and probe lasers, producing wavelengths of 1470 and 1530 nm, respectively, together with a reflected radiation detector. Heat pump pulse duration varies from a few microseconds to tens of microseconds. The potential of the pump-probe TR-FP technique to investigate the subsurface region of semiconductors with a range of electron spectra is demonstrated. A pronounced dip in time dependence of the TR-FP signal is discovered at the liquid nitrogen temperature in the gapless semiconductor compound HgSe—a candidate for the family of Weyl semimetals with broken inversion symmetry. This finding implies the developed pulsed TR-FP method for the detection of Weyl nodes and surface Fermi arcs in solids.     

一套高温高压原位拉曼散射、布里渊散射测量系统

本文描述了一套利用激光加热技术、金刚石对顶砧高压技术,集成共聚焦拉曼光谱测量、六通道布里渊散射光谱测量、以及黑体辐射光谱测温,成功搭建起来的高温高压原位拉曼散射、布里渊散射的光学测量系统。利用该系统,并结合薄膜沉积金属、光刻技术改进了金刚石对顶砧中样品的装填方法,解决了样品透明不易加热的问题。已利用该系统得到液态氩在0.85 GPa常温状态下和14.58 GPa熔融状态下的体声速分别为1.85 Km/s和5.19 Km/s。     

Constant electrical resistivity of Zn along the melting boundary up to 5 GPa

We measured the electrical resistivity of high purity Zn along the melting boundary, up to 5?GPa in a large volume press. The electrical resistivity remained constant on the melting boundary, as predicted in a thermodynamics-based model for simple metals. The effects of pressure and temperature on the electrical resistivity of the solid and liquid states are interpreted in terms of their antagonistic effects on the electronic structure of Zn. Within the error of measurements, our melting temperature data agree well with those of the previous studies. The electronic thermal conductivity was calculated from resistivity data using the Wiedemann–Franz law and shows a decrease with temperature in the solid state and an increase in the liquid state, with a large decrease on melting. Comparison of calculated electronic and measured total thermal conductivities indicates that the electronic component dominates over the phonon component in Zn.     

Are there phase transitions in liquid metallic alloys?

Recently, resistivity measurements of some liquid metals and metallic alloys have been obtained using an electrode technique. A marked change of the slope of the resistivity versus temperature has been observed following the history of the alloy in the liquid state and the authors conclude that there are “structural transitions in the melt”. It is of interest to examine such effects and to try to understand their origin. In this work, the resistivities of several liquid metals and metallic alloys were measured as a function of temperature. Particular attention was given to the history of the alloy, including solidification and melting conditions. We also observed “anomalies”. Our experiments lead us to conclude that they must very probably be attributed to the release of gas or vapour bubbles in the liquid alloy at the first heating, resulting from the decomposition of compounds like oxides or hydroxides of the metals, but not from a phase transition in the liquid metallic state involving “breaking” Sn–Sn covalent bands.     

Shock metamorphism of the graphite quasimonocrystal

Abstract

Micro structure examination of graphite quasimonocrystal recovered after dynamic loading to pressure of 35-45 GPa was carried out. Only a small amount of cubic diamond and recrystalized graphite was detected. Most of the graphite (～80 vol.%) remained in initial high orientation, but transformed to fine, grained phase with crystalite size 0.1-1 microns. Relaxation time of the transformation (～ 10 ns) and the degree of the transformation (～ 70-80 vol.%) were determined by means of measurements of the electrical resistivity during loading up to 26 GPa and following computer simulation of the results. We proposed that two simultaneous processes take place at pressures higher than 20 GPa: i) relatively slow diffusive graphite to diamond transformation localized in the zones with defect structure: ii) highly oriented graphite transforms to a diamond like phase with density of about 3.2 g/cm³ at zero pressure. This, transformation has fast, martensitic kinetics and is reversible.     

Graphite at high pressures: Pseudomelting at 44 GPa

Abstract

The Raman spectra comparative study of graphite-like modifications of carbon: monocrystalline graphite, pyrolytic graphite and amorphous (glassy) carbon was performed at high pressures and room temperature. At P = 44 GPa an abrupt broadening of Raman bands of pyrolytic graphite and glassy carbon was observed. The same process in monocrystalline graphite occures continuously from 23 to 44 GPa and for higher pressures the Raman spectra of all three substances under study become practically indistinguishable from one another and from that of amorphous carbon (a-C) at the same pressure. This result is ascribed to the formation at these pressures of the dence amorphous carbon modification.     

Gas-dynamic consideration of the laser evaporation synthesis of single-wall carbon nanotubes

The abundance of carbon single-wall nanotubes (SWNTs) in soot synthesized by pulsed laser evaporation of graphite is studied over a wide range of synthesis conditions. The derived SWNT growth time-scale appears to be much longer than any characteristic time-scale in a simplified model of the relaxation of a high-pressure hot condensing gas bubble in a background atmosphere. It is concluded that SWNT nucleation and growth take place in relaxed, condensed, thermalized evaporation products at an optimal temperature between 850-1250 °C at a rate of few 7m length per second, which is consistent with a condensed state "precipitation" mechanism for the SWNT formation.     

Equation of state and electrical resistivity of liquid mercury at elevated temperatures and pressures

Experimental results have been obtained for the density and electrical resistivity of liquid mercury as functions of the independent variables temperature (20°c–1000°c) and pressure (0–1000 bars). Basic equipment for both measurements consisted of a steel vessel containing an internal electrical resistance furnace and pressurized with argon gas. The equation of state was determined with an accuracy of about ±1/4% using Archimedes' method by employing a series of totally immersed radioactive sinkers whose rise or fall in the mercury was detected with a γ-ray counter external to the pressure vessel. The electrical resistivity was measured with an accuracy of about ±1/2% using a four-lead resistance cell fabricated in fused silica. The two measurements have also been combined to give electrical resistivity at constant volume.     

Temperature as a key parameter for graphene sono-exfoliation in water

Graphene dispersions in water are highly desirable for a range of applications such as biomedicines, separation membranes, coatings, inkjet printing and more. Recent novel research has been focussed on developing a green approach for scalable production of graphene. However, one important parameter, which is often neglected is the bulk temperature of the processing liquid. This paper follows our earlier work where optimal sono-exfoliation parameters of graphite in aqueous solutions were determined based on the measured acoustic pressure fields at various temperatures and input powers. Here, we take the next step forward and demonstrate using systematic characterisation techniques and acoustic pressure measurements that sonication-assisted liquid phase exfoliation (LPE) of graphite powder can indeed produce high quality few layer graphene flakes in pure water at a specific temperature, i.e. 40 °C, and at an optimised input generator power of 50%, within 2-h of processing. UV–vis analysis also revealed that the exfoliation, stability and uniformity of dispersions were improved with increasing temperature. We further confirmed the successful exfoliation of graphene sheets with minimal level of defects in the optimized sample with the help of Raman microscopy and transmission electron microscopy. This study demonstrated that understanding and controlling processing temperature is one of the key parameters for graphene exfoliation in water which offers a potential pathway for its large-scale production.     

High pressure behaviour of liquid caesium

This paper deals with the anomalous behaviour of liquid caesium at high pressures. A model for the phenomenon of electron collapse in the liquid phase, based on the anomalous density variation of liquid caesium with pressure has been proposed. The process of 6s→5d electron collapse is pictured as the formation of a virtual bound state and the tunnelling process accounts for the 6s⇌5d dynamic conversion. The same model together with the Friedel sum rule has been used to explain the resistivity variation of liquid caesium with pressure. The resistivity minimum observed in most of the liquid alkali metals in the low pressure region has been explained. The agreement with the experimental curve is good in the low pressure region whereas a large discrepancy exists at higher pressures. This may be due to the breakdown of the Ziman’s resistivity formula under conditions of resonance scattering.     

Dc electrical conductivity of Ge2S3Agx glasses at high hydrostatic pressure

The paper deals with the influence of hydrostatic pressure on d.c. electrical conductivity in Ge₂S₃Ag _x glasses forx10%. The initial material exhibits high resistivity and the presence of Ag impurity yields strong increase in electrical conductivity. The experimental results suggest that there is a non-linear decrease of electrical resistivity at pressure ranging from 0·1 to 10³ MPa. The pressure coefficient of resistivity is a function ofx. All measurements were performed on bulk samples using graphite contacts. The experimental results are interpreted by means of ionic conductivity.     

Ultra fine carbon nitride nanocrystals synthesized by laser ablation in liquid solution

Crystalline carbon nitride nanopowders and nanorods have been successfully synthesized at room temperature and pressure using the novel technique of pulsed laser ablation of a graphite target in liquid ammonia solution. High-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and Fourier transform infrared spectroscopy (FTIR) were used to systematically study the morphology, nanostructure and chemical bonding. The experimental composition and structure of the nanoparticles are consistent with the theoretical calculations for α-C₃N₄. After 2 h ablation the particles had a size distribution ∼8–12 nm, whereas after 5 h ablation the particles had grown into nanorod-like structures with a crystalline C₃N₄ tip. A formation mechanism for these nanorods is proposed whereby nanoparticles are first synthesized via rapid formation of an embryonic particle, followed by a slow growth, eventually leading to a one-dimensional nanorod structure.