Volume and structural study of Fe64Mn36 anti-ferromagnetic Invar alloy under high pressure

We have investigated the pressure variation of the volume and structure of an FCC Fe₆₄Mn₃₆ anti-ferromagnetic Invar alloy. The inclination of the pressure-volume (P-V) curve of the FCC structure becomes discontinuous at a pressure of 4 GPa. According to the bulk modulus at zero pressure estimated by the Birch-Murnaghan equation of state, the pressure between 4 and 10 GPa is 33 GPa larger than that at a pressure below 4 GPa. Considering previous experiments on magnetism at high pressure the Neel temperature at 4 GPa almost decreases to room temperature. These results suggest that the increase in the bulk modulus by 33 GPa can be attributed to the pressure-induced magnetic phase transition from anti-ferromagnetism to paramagnetism. Volume at zero pressure was estimated using the Birch-Murnaghan equation of state. The volume of FCC structure in the anti-ferromagnetic state was 1.17% larger than the volume in the paramagnetic state, namely, the spontaneous magnetostriction was 1.17%. Pressure-induced structural transition from FCC to HCP occurs with an increase in the pressure, especially at up to 5 GPa. The value of c/a is 1.62; this value almost corresponds to that of an ideal HCP structure. The bulk modulus of the HCP structure estimated by the Birch-Murnaghan equation of state is larger than that of the FCC structure, and the volume/atom ratio is smaller than that of the FCC structure.     

Effect of deformation of diamond anvil and sample in diamond anvil cell on the thermal conductivity measurement

Studies show that the sample thickness is an important parameter in investigating the thermal transport properties of materials under high-temperature and high-pressure (HTHP) in the diamond anvil cell (DAC) device. However, it is an enormous challenge to measure the sample thickness accurately in the DAC under severe working conditions. In conventional methods, the influence of diamond anvil deformation on the measuring accuracy is ignored. For a high-temperature anvil, the mechanical state of the diamond anvil becomes complex and is different from that under the static condition. At high temperature, the deformation of anvil and sample would be aggravated. In the present study, the finite volume method is applied to simulate the heat transfer mechanism of stable heating DAC through coupling three radiative-conductive heat transfer mechanisms in a high-pressure environment. When the temperature field of the main components is known in DAC, the thermal stress field can be analyzed numerically by the finite element method. The obtained results show that the deformation of anvil will lead to the obvious radial gradient distribution of the sample thickness. If the top and bottom surfaces of the sample are approximated to be flat, it will be fatal to the study of the heat transport properties of the material. Therefore, we study the temperature distribution and thermal conductivity of the sample in the DAC by thermal-solid coupling method under high pressure and stable heating condition.     

Stress‐induced Curie temperature increase in the Fe64Ni36 invar alloy

Structural and magnetic changes on invar Fe₆₄Ni₃₆ alloy (T_C = 500 K) produced by mechanical milling followed by heating up to 1073 K, were investigated by neutron diffraction, magnetization measurements, X‐ray diffraction under high pressures and X‐ray absorption at both Fe and Ni K‐edges. We argue that the strain induced in the Fe₆₄Ni₃₆ material after this treatment mainly affects the Fe sites due to the magnetovolume coupling, the most notorious feature being the increase of the Curie temperature (ΔT_C = 70 K). (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Compression and shear on lead in a rotational diamond anvil cell

By application of large plastic shear on a lead sample in a rotational diamond anvil cell, we studied the pressure self-multiplication and the stress deviation phenomena, along with the consequential effects on a phase transformation of lead. It is indicated that pressure can be promoted by the gradual addition of shear. The stress deviation in the sample along different Chi angles is minimal and within the systematic error range. It is thus specified that a quasi-hydrostatic condition is generated in the sample chamber. Moreover surprisingly, under such shear-controlled pressure elevation, the lead fcc-to-hcp phase transformation pressure is found to initiate and complete, respectively, at 12.8 and 18.5?GPa, which is identical to those observed in hydrostatic compressions. The phenomena of the so-launched quasi-hydrostatic pressure, the self-multiplication, along with the consequential effects on the phase transformation properties by shear at pressures are expected to lead to further understanding of materials as well as to potential new technologies at extremes.     

Formation and characterization of boride coatings thermochemically grown on the Fe64Ni36 alloy

Zirconium oxide (zirconia) exists in three crystalline forms of monoclinic, tetragonal and cubic structures at atmospheric pressures. The cubic form of zirconia is well known for its mechanical, electrochemical and optical applications. Fe-doped cubic zirconia (high temperature phase) compositions are synthesized by microwave combustion method. Here, we present a Mössbauer investigation of Zr_1???x Fe _x O₂ composition within a range of Fe (0.03 < x < 0.09). ⁵⁷Fe Mössbauer spectra were recorded at room temperature and at low temperature (77 K) for all samples. 3% Fe-doped ZrO₂ shows doublet and the corresponding 6% and 9% Fe-doped ZrO₂ samples show superimposed sextet and doublets. The isomer shift and quadrupole moment indicate, Iron to be in III oxidation state and to occupy different octahedral sites, associated with some amount of disorder. X-ray powder diffraction pattern of Fe-doped ZrO₂ samples appear as very well crystalline. The Miller indices refer to the cubic fluorite-type ZrO₂ structure. The magnetic behavior shows increase in moment and decrease in coercivity, with increase in Fe concentration. The M vs. H plots of the as-prepared Zr_1-x Fe _x O₂ essentially show typical hysteresis loops, indicating room temperature ferromagnetism. Thus, the introduced microwave combustion route is an effective process to achieve multifunctional Fe-doped Zirconia with coexistent magnetic properties.     

Evidence of new high-pressure magnetic phases in Fe–Pt Invar alloy

To investigate the magnetic properties of disordered Fe₇₀Pt₃₀ Invar alloy under high pressure, measurements of the real part of the AC susceptibility (χ) were made under pressure up to 7.5 GPa in the temperature range 4.2–385 K using a cubic anvil high-pressure apparatus. The Curie temperature (T_C) decreased with increasing pressure, and then, two new high-pressure magnetic phases appeared. These results show that the ferromagnetism of Fe–Pt Invar alloy becomes weaker, and the antiferromagnetic interaction becomes dominant with increasing pressure.     

Mössbauer analysis and magnetic properties of Invar Fe–Ni–C and Fe–Ni–Mn–C alloys

The saturation magnetization and the hyperfine magnetic field of different f.c.c. Fe–Ni based alloys containing nearby 29 at .% Ni were studied as a function of temperature and for different Carbon and Manganese contents. We have observed abnormal behaviors that are explained in terms of mixed exchange interactions between atomic spins: J _NiNi(r _i ) < 0, J _FeFe(r _i ) > 0, J _NiFe(r _i ) < 0.     

How to detect melting in laser heating diamond anvil cell

Research on the melting phenomenon is the most challenging work in the high pressure/temperature field. Until now,large discrepancies still exist in the melting curve of iron, the most interesting and extensively studied element in geoscience research. Here we present a summary about techniques detecting melting in the laser heating diamond anvil cell.     

Development of micro‐XANES mapping in the diamond anvil cell

Energy‐dispersive X‐ray absorption spectroscopy is now a well established method that has been applied to a broad range of applications. At the energy‐dispersive EXAFS beamline of the ESRF, ID24, the recently achieved 5 × 5 µm focal spot combined with fast acquisition has allowed complex and non‐uniform samples to be mapped and images to be obtained where each pixel contains full XAS information. This method has been applied to a study under extreme conditions of pressure and temperature in a diamond anvil cell in transmission mode. The case study was the investigation of the Fe K‐edge XANES of (Mg,Fe)SiO₃‐perovskite and (Mg,Fe)O‐ferropericlase on decomposition of the spinel‐structured olivine [γ‐(Mg,Fe)₂SiO₄] at 78 (3) GPa after laser heating at 2200 (100) K.     

Thickness dependence of magnetization in FeNi invar alloy film

The thickness dependence of magnetization of FeNi Invar alloy films was observed by means of small angle Lorentz electron diffraction. A remarkable reduction of magnetization at room temperature was observed for films with thickness below 400 Å. This may be ascribable to the instability of the ferromagnetic state in Fe-Ni Invar alloys.     

金刚石压腔蛇纹石原位拉曼光谱研究

在金刚石压腔中,运用激光拉曼光谱技术对高压下蛇纹石矿物结构及其稳定性进行了原位观测与研究。实验获得蛇纹石在常温下从0.1～5 140MPa的拉曼光谱数据。研究发现,蛇纹石低频拉曼谱峰388,471,692和705cm-1随压力增加有规律地向高频偏移;层内羟基3 664cm-1峰和层间羟基3 696cm-1峰与压力呈明显的正相关性。层内羟基3 664cm-1峰随压力变化的斜率为3.3cm-1.GPa-1,层间羟基3 696cm-1峰在2.0GPa时斜率由8.3cm-1.GPa-1变为1.1cm-1.GPa cm-1。在实验温压条件下,蛇纹石未发生脱水作用。     

Magnetic field analysis in a diamond anvil cell for Meissner effect measurement by using the diamond NV~- center

Diamond negatively charged nitrogen-vacancy(NV-) centers provide an opportunity for the measurement of the Meissner effect on extremely small samples in a diamond anvil cell(DAC) due to their high sensitivity in detecting the tiny change of magnetic field. We report on the variation of magnetic field distribution in a DAC as a sample transforms from normal to superconducting state by using finite element analysis. The results show that the magnetic flux density has the largest change on the sidewall of the sample, where NV-centers can detect the strongest signal variation of the magnetic field. In addition, we study the effect of magnetic coil placement on the magnetic field variation. It is found that the optimal position for the coil to generate the greatest change in magnetic field strength is at the place as close to the sample as possible.     

X-ray transmission properties of intelligent anvils in diamond anvil cells

High-pressure and/or high-temperature analysis of geo- and material science samples routinely employs diamond anvil cells (DACs) as a research instrument. In particular, DACs allow for various in situ characterizations (e.g. Raman and Fourier transform infra red spectroscopies, X-ray diffraction (XRD), X-ray spectroscopy including fluorescence (XRF) and absorption (XAS)) at elevated pressure and temperature. The measurement of pressure (P) and/or temperature (T) in the sample chamber is crucial, but not always accurate, more specifically in the case of low-pressure applications (a few GPa). The development of modified diamonds (intelligent anvils ‘i-anvils’) adapted to a new generation of DACs (intelligent diamond anvil cells: iDAC) can contribute to solve this problem, as the diamond itself serves as the PT sensor, being prepared, for example, by high-energy ion implantation [H. Bureau, M. Burchard, S. Kubsky et al., This volume (2006).] on a micrometric scale. Several most interesting measurement methods used with DACs are based on X-ray techniques (e.g. XRF, XRD, XAS). We present the first results of X-ray transmission measurements with iDACs, performed at the hard-X-ray microfocus beamline ID22 at the ESRF (European Synchrotron Radiation Facility), Grenoble, France. Sensor response to intense irradiation as a function of X-ray energy (E _ph∈10;18.1 Burchard, M., Zaitsev, A. M. and Maresh, W. 2003. Rev. Sci. Instr., 74: 1263–1266.  [Google Scholar] keV) was investigated. The values of the sensor were found to be independent of the irradiation in the investigated energy range and thus validate the use of these sensors for precise and reliable measurements on a wide range of applications with high-energy synchrotron radiation. No influence of the sensor on the X-ray transmission properties of the anvil has been found.     

Anvil design for slip-free high pressure deformation experiments in a rotational diamond anvil cell

A rotational diamond anvil cell is the most suitable deformation apparatus with which to investigate the rheological properties of deep-Earth materials at pressures similar to those found in the lower mantle and core. However, slip between the sample and piston is still a problem, since the slip prevents the attainment of a constant strain rate and interferes with the uniform deformation of a sample. In this paper, we report that using a diamond anvil with deep grooves results in a marked improvement in the coupling between the sample and the diamond anvils.     

Suppression of Bragg reflection glitches of a single‐crystal diamond anvil cell by a polycapillary half‐lens in high‐pressure XAFS spectroscopy

In combination with a single‐crystal diamond anvil cell (DAC), a polycapillary half‐lens (PHL) re‐focusing optics has been used to perform high‐pressure extended X‐ray absorption fine‐structure measurements. It is found that a large divergent X‐ray beam induced by the PHL leads the Bragg glitches from single‐crystal diamond to be broadened significantly and the intensity of the glitches to be reduced strongly so that most of the DAC glitches are efficiently suppressed. The remaining glitches can be easily removed by rotating the DAC by a few degrees with respect to the X‐ray beam. Accurate X‐ray absorption fine‐structure (XAFS) spectra of polycrystalline Ge powder with a glitch‐free energy range from ?200 to 800 eV relative to the Ge absorption edge are obtained using this method at high pressures up to 23.7 GPa, demonstrating the capability of PHL optics in eliminating the DAC glitches for high‐pressure XAFS experiments. This approach brings new possibilities to perform XAFS measurements using a DAC up to ultrahigh pressures.     

Synthesis of Ge-Sn at high pressure and high temperature in a laser-heated diamond anvil cell

Ge–Sn compound is predicted to be a direct band gap semiconductor with a tunable band gap. However, the bulk synthesis of this material by conventional methods at ambient pressure is unsuccessful due to the poor solubility of Sn in Ge. We report the successful synthesis of Ge–Sn in a laser-heated diamond anvil cell (LHDAC) at ~7.6 GPa &; ~2000 K. In situ Raman spectroscopy of the sample showed, apart from the characteristic Raman modes of Ge TO (Г) and β-Sn TO (Г), two additional Raman modes at ~225 cm^?1 (named Ge–Sn₁) and ~133 cm^?1 (named Ge–Sn₂). When the sample was quenched, the Ge–Sn₁ mode remained stable at ~215 cm^?1, whereas the Ge–Sn₂ mode had diminished in intensity. Comparing the Ge–Sn Raman mode at ~225 cm^?1 with the one observed in thin film studies, we interpret that the observed phonon mode may be formed due to Sn-rich Ge–Sn system. The additional Raman mode seen at ~133 cm^?1 suggested the formation of low symmetry phase under high P–T conditions. The results are compared with Ge–Si binary system.     

Abrupt discontinuity of the bulk modulus pressure dependence in Fe64Ni36

X-ray diffraction and ultrasonic measurements have been carried out simultaneously up to 7 GPa at ambient temperature on a polycrystalline sample of Fe64Ni36 Invar alloy. The bulk modulus is found to increase linearly with pressure with an unusual low value (1.4) of dB/dP up to about 3.1(2) GPa followed by a regular slope (3.6) at higher pressure. The observation of these two distinct regimes is in qualitative agreement with previous results on the variation of the iron magnetic moment, and can be interpreted using the 2gamma-state model in terms of gradual population of low spin-small volume state at the expense of the high spin-large volume state under pressure.     

Measurement of thermal conductivity in laser-heated diamond anvil cell using radial temperature distribution

ABSTRACT

Thermal conductivities of planetary materials under extreme conditions are important input parameters for modeling planetary dynamics such as accretion, geodynamo and magnetic field evolution, plate tectonics, volcanism-related processes etc. However, direct experimental measurements of thermal conductivity at extreme conditions remain challenging and controversial. Here we propose a new technique of thermal conductivity measurement in laser-heated diamond anvil cell (LH-DAC) based on radial temperature distribution around laser focal spot, mapped by imaging tandem acousto-optical tunable filter (TAOTF). The new technique provides much more information about heat fluxes in the laser-heated sample than existing static heating setups, and does not require dynamic numerical modeling using heat capacities in contrast to dynamic pulsed heating setups. In the test experiment, thermal conductivity of γ-Fe at conditions relevant to cores of terrestrial planets was measured.     

Three-dimensional X-ray diffraction in the diamond anvil cell: application to stishovite

Three-dimensional X-ray diffraction can be used for characterizing the orientation, position, and strain tensor of single grains in a polycrystalline aggregate. Here, we show how the method is well suited for diamond anvil cell data with heterogeneous grain sizes, with an application to two samples of stishovite at 15 and 26 GPa. For each grain, we obtain a well-defined orientation matrix and cell parameters. Center of mass position can also be adjusted to the experimental data, with errors in the present experiment. Finally, strain tensors are adjusted for the individual grains. The stress distribution obtained is in agreement with expectations from the diamond anvil cell geometry and previous measurements of stishovite strength. Advantages and potential for improvement of the method are then discussed.