High Pressure Melting Studies in Diamond Cells

Guoyin Shen
Consortium for Advanced Radiation Sources, University of Chicago, Chicago, USA; shen@cars.uchicago.edu

Data from high pressure melting experiments provide two important pieces of information to Earths convention models. One is the depth dependence of the viscosity, because it scales with the homologous temperature (the ratio of the temperature to the melting temperature) [Weertman and Weertman, 1975]. The other is the temperature profile of the Earths interior [see reviews by Williams, 1998 and Boehler, 2000]. The high pressure melting of iron is probably the most extensively studied subject, because it provides a first order constraint on the temperature of the core. Estimates rely on the assumption that the boundary between the solid inner core and the liquid outer core is at the melting temperature of the core material. The temperature at the core mantle boundary (CMB) may be constrained by three primary parameters: the temperature at the 670 km discontinuity; the temperature at the inner coreouter core boundary (IOB); and the adiabatic temperature gradients within the Earths lower mantle and the outer core. Information of these primary parameters could be obtained through studies on phase transitions responsible for the 670-km discontinuity, high pressure melting of iron and iron alloys, and thermodynamic properties of major minerals in the lower mantle and the outer core. In recent years, the generation and measurement of simultaneous high pressures and high temperatures has undergone rapid development with the diamond anvil cell (DAC) technique [e.g., Mao and Hemley, 1996; Boehler, 2000; Shen et al., 2001a]. The amount of available data on melting behavior at high pressure is increasing. However, considerable controversy has surrounded the determination of the melting temperature, e.g., of iron at P > 30 GPa. The melting determination in DAC experiments has been a subject of many articles [Duba, 1994; Jeanloz and Kavner, 1996; Lazor and Saxena, 1996]. Recently, Boehler [2000] pointed out the emerging convergence of static data on high pressure melting of iron, and stated that it may be difficult to significantly expand the pressure range and accuracy of melting experiments in the diamond anvil cell. Here I argue that we are actually at a breakthrough of a significant increase in accuracy of melting experiments, by examining a critical issue: the melting criteria. In fact, the recent data from synchrotron experiments [Hemley and Mao, 2001; Ma et al., 2001] show that the melting temperature of iron is about 700 K higher than that by Boehler [2000] at 105 GPa and the extrapolated melting curve yields 1000 K difference in melting temperature at the IOB (Fig. 1). Melting is thermodynamically defined as equilibrium between a solid and a liquid. When materials melt, their physical properties, such as density, viscosity, absorption properties, and electrical resistance, involve a sudden change. Such property changes are characteristic for a first order phase transition and are often used for recognition of melting. Different from other first order phase transitions, melting is characterized by the loss of long-range order and resistance to shear. To definitively identify melting, one or both of these two characteristics should be documented. Jeanloz and Kavner [1996] reviewed five types of melting criteria in

laser heated DAC experiments, namely fluid flow, glass formation, quench texture, change in sample properties, and temperature-verses-laser-power correlation, and concluded that the most reliable criteria for determining melting inside the laser heated DAC are fluid flow and quenched glass formation. It is true that fluid flow observation is a good measure of the loss of resistance to shear. Therefore it has been considered as one of the best criteria and widely used by almost all groups in the world. [Boehler, 2000; Jephcoat and Besedin, 1996; Saxena et al., 1994; Shen et al., 1993; Sweeney and Heinz, 1998]. Shen et al. [1993] pointed out that visual observation (fluid flow) is less obvious as pressure increases; above 40 GPa (where the lack of agreement starts) there exists a large temperature gap of a few hundreds degrees between occasional small movement (not fluid flow) and fluid-like motion, making it difficult to unambiguously define the onset of melting. The subjective nature of visual observation may account for the inconsistent results in literature. Another way to document the loss of rigidity is the use of Brillouin spectroscopy, which is still under development. Synchrotron xray diffraction has been combined with laser heated DAC and used for melting studies to document the loss of long range order upon melting [Ma et al., 2001; Shen et al., 1998]. The appearance of diffraction peaks at a certain pressure-temperature condition clearly indicates the presence of a crystalline phase. However, a simple loss of diffraction peaks is not necessarily indicative of melting due to insufficient statistics arising from possible crystal growth and small x-ray beam size. Shen et al. [1998] cautioned that the conclusive identification of melts is still limited by the energy dispersive x-ray diffraction technique. Recently, an area detector with a monochromatic x-ray beam was successfully used for melting determination in a diamond anvil cell. Melting at high pressure was identified by the appearance of diffuse scattering from the melt with the simultaneous loss of crystalline diffraction signals [Shen et al., 2001b]. The new method relies on positive signals (diffuse scattering) together with a measure of the characteristic property of melting (loss of long range order), providing an objective way of signifying melting and an important extension of the visual observation method (Fig. 2). The observation of the diffuse scattering has also been applied to studies of structure factors and molar volumes of melts at high pressures and high temperatures [Shen et al., 2001c; Shen et al., 2001d]. For metals, melting is found to be reversible (Fig. 2e), so that the same sample can be used again in a single run at different pressures. For glass forming materials, cautions should be taken by paying attentions to the experimental pressure-temperature paths. Efforts are currently being made on melting studies of Earth materials utilizing an area detector and micro-x-ray beam to expand the pressure with the double sided laser heated DAC. Unambiguous phase identification requires the x-ray probe, heating laser beams, and samples to be aligned to the same point. It is conceptually simple, but rather challenging in practice. Under intense heating for melting studies, maintaining the alignment for the entire system requires large efforts. The possible sample diffusion at high temperatures close to melting further complicates the x-ray analysis. Diffuse wings of the x-ray beam may pick up additional diffraction peaks from materials outside the area of interest. All these difficulties need to be overcome for high accuracy of melting studies. The progress is going on and it is believed that accurate data on high pressure melting with definite melting recognition will emerge in the near future. In recent years, nuclear resonant x-ray scattering techniques that utilize synchrotron radiation have made great progresses in the study of vibrational and magnetic properties of condensed matter under extreme conditions [Burkel, 2000; Mao et al., 2001]. In particular for

melting studies, data from nuclear forward scattering (Mssbauer effect) provide measures of atomic thermal displacement, which can be used for documenting rigidity of a material. Upon melting strong elastic resonance signal diminishes in the nuclear forward scattering. Mean square thermal displacement of atoms (Lamb-Mssbauer factor) can be measured as a function of temperature, providing a plot for determining the onset of melting. By combining the nuclear resonance inelastic x-ray scattering (NRIXS), temperatures can be directly measured from the scattering data, complementary to those measurements by thermal radiation and/or thermocouples. Since measurement of nuclear forward scattering takes only a few seconds to minutes, it holds a great potential for high pressure melting studies.

Fig. 1 Phase diagram of iron determined by synchrotron x-ray diffraction/double sided laser heating experiments. The thick solid lines are from double sided laser heating studies [Shen et al., 1998]. The experiment has been extended to a pressure of 161 GPa recently [Ma et al., 2001]. The points correspond to regions where the indicated phases were observed. Data with symbols of solid circle, open squares and diamonds are from Shen et al; triangles are from [Ma et al., 2001]. Solid squares with error bars are shock wave data from [Brown and McQueen, 1986]. Extrapolation of the synchrotron data (thin solid line) is based on Lindemans law [Ma et al., 2001], resulting in a melting temperature of 5800(200) K at the IOB. Theory data are from: 1-Laio et al. [2000], 2-Alfe et al. [1999], and 3-Belonoshko et al. [2000]. Data from Boehler [2000] and Williams [1998] are shown as dashed lines.

(e)

Fig. 2 (Color) X-ray scattering images and their integrated pattern at the onset of melting of indium at about 2 GPa Two sharp rings are the diffraction of medium material (NaCl). (a) Crystalline indium shows a spotty pattern at 519(1) K. (b) The indium diffraction spots fade out and diffuse scattering starts to appear at 526(1). (c) A clear homogeneous diffuse ring of the melt can be seen at 531(1) K. (d) Integrated patterns by FIT2D for images from (a) to (c). A broad diffuse band can be clearly seen in the vicinity of indium (101). (e) Intensity change of the diffuse scattering band at the onset of melting. Solid circles are the data upon heating; while crosses are those on cooling. A sharp change in intensity occurs in the same temperature region upon both heating and cooling, indicating the melting is reversible. Lines are freehand fits for eyes. (after Shen et al., 2001b). Acknowledgments: This work is supported by NSF-EAR 00011498. The GSECARS sector is supported by the NSF, DOE and the W. M. Keck Foundation. References: Alfe, D., M.J. Gillan, and G.D. Price, The melting curve of iron at pressures of the Earth's core from ab initio calculations, Nature, 401, 462-464, 1999. Belonoshko, A.B., R. Ahuja, and B. Johansson, Quasi-ab initio molecular dynamics study of Fe melting, Phys. Rev. Lett., 16, 3638-3641, 2000. Boehler, R., High pressure experiments and the phase diagram of lower mantle and core materials, Rev. Geophysics, 38, 221-245, 2000. Brown, J.M., and R.G. McQueen, Phase transitions, Gruneisen parameter and elasticity for shocked iron between 77 GPa and 400 GPa, J. Geophys. Res, 91, 7485-7494, 1986. Burkel, E., Phonon spectroscopy by inelastic x-ray scattering, Rep. Prog. Phys., 63, 171-232, 2000.

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