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Sample records for olivines limnpo4 lifepo4

  1. Basic Electrochemical Performance of Pure LiMnPO4: a Comparison with Selected Conventional Insertion Materials.

    PubMed

    Moškon, Jože; Pivko, Maja; Miran, Gaberščk

    2016-01-01

    We compare the basic electrochemical performance of a LiMnPO4 battery material with the performance of its much more researched olivine counterpart - LiFePO4. To get a wider picture, we also included another well understood material, LiCoO2. Based on chronopotentiometric (galvanostatic) experiments, we discuss the materials performance in terms of cell energy efficiency and electrode polarization. We propose and justify the use of the "inflection point criterion" for determination of total overpotential (ηtotal). We further demonstrate that the general current-overpotential characteristics can be represented by introducing the total resistance of the cell - Rtotal.We find consistently that whereas in LCO the general current-overpotential characteristics is more or less linear, there is significant deviation from linearity in LiFePO4 and even bigger in LiMnPO4. The phenomenon is discussed in terms of state-of-the art knowledge about phase transformation phenomena in these materials. PMID:27640373

  2. Advanced carbon materials/olivine LiFePO4 composites cathode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Gong, Chunli; Xue, Zhigang; Wen, Sheng; Ye, Yunsheng; Xie, Xiaolin

    2016-06-01

    In the past two decades, LiFePO4 has undoubtly become a competitive candidate for the cathode material of the next-generation LIBs due to its abundant resources, low toxicity and excellent thermal stability, etc. However, the poor electronic conductivity as well as low lithium ion diffusion rate are the two major drawbacks for the commercial applications of LiFePO4 especially in the power energy field. The introduction of highly graphitized advanced carbon materials, which also possess high electronic conductivity, superior specific surface area and excellent structural stability, into LiFePO4 offers a better way to resolve the issue of limited rate performance caused by the two obstacles when compared with traditional carbon materials. In this review, we focus on advanced carbon materials such as one-dimensional (1D) carbon (carbon nanotubes and carbon fibers), two-dimensional (2D) carbon (graphene, graphene oxide and reduced graphene oxide) and three-dimensional (3D) carbon (carbon nanotubes array and 3D graphene skeleton), modified LiFePO4 for high power lithium ion batteries. The preparation strategies, structure, and electrochemical performance of advanced carbon/LiFePO4 composite are summarized and discussed in detail. The problems encountered in its application and the future development of this composite are also discussed.

  3. Comparison of electrochemical performances of olivine NaFePO4 in sodium-ion batteries and olivine LiFePO4 in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Yujie; Xu, Yunhua; Liu, Yihang; Luo, Chao; Wang, Chunsheng

    2012-12-01

    Carbon-coated olivine NaFePO4 (C-NaFePO4) spherical particles with a uniform diameter of ~80 nm are obtained by chemical delithiation and subsequent electrochemical sodiation of carbon-coated olivine LiFePO4 (C-LiFePO4), which is synthesized by a solvothermal method. The C-NaFePO4 electrodes are identical (particle size, particle size distribution, surface coating, and active material loading, etc.) to C-LiFePO4 except that Li ions in C-LiFePO4 are replaced by Na ions, making them ideal for comparison of thermodynamics and kinetics between C-NaFePO4 cathode in sodium-ion (Na-ion) batteries and C-LiFePO4 in lithium-ion (Li-ion) batteries. In this paper, the equilibrium potentials, reaction resistances, and diffusion coefficient of Na in C-NaFePO4 are systematically investigated by using the galvanostatic intermittent titration technique (GITT), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV), and compared to those of the well-known LiFePO4 cathodes in Li-ion batteries. Due to the lower diffusion coefficient of Na-ion and higher contact and charge transfer resistances in NaFePO4 cathodes, the rate performance of C-NaFePO4 in Na-ion batteries is much worse than that of C-LiFePO4 in Li-ion batteries. However, the cycling stability of C-NaFePO4 is almost comparable to C-LiFePO4 by retaining 90% of its capacity even after 100 charge-discharge cycles at a charge-discharge rate of 0.1 C.Carbon-coated olivine NaFePO4 (C-NaFePO4) spherical particles with a uniform diameter of ~80 nm are obtained by chemical delithiation and subsequent electrochemical sodiation of carbon-coated olivine LiFePO4 (C-LiFePO4), which is synthesized by a solvothermal method. The C-NaFePO4 electrodes are identical (particle size, particle size distribution, surface coating, and active material loading, etc.) to C-LiFePO4 except that Li ions in C-LiFePO4 are replaced by Na ions, making them ideal for comparison of thermodynamics and kinetics between C-NaFePO4 cathode in

  4. High-performance, nanostructure LiMnPO4/C composites synthesized via one-step solid state reaction

    NASA Astrophysics Data System (ADS)

    Zheng, Jugong; Ni, Liang; Lu, Yanwen; Qin, Cancan; Liu, Panxing; Wu, Tongfu; Tang, Yuefeng; Chen, Yanfeng

    2015-05-01

    LiMnPO4 is proposed as more promising cathode material as LiFePO4, while poor electronic conductivity and Jahn-Teller effects during charge/discharge processes hinder the electrochemical performance. To overcome these problems, one-step solid state reaction method is developed to synthesize LiMnPO4/C composites, which is with nanostructure, high crystallinity and good carbon coating. Manganese oxide sources and calcination temperature are investigated as factors for preparing high-performance LiMnPO4/C for Li-ion batteries. The results show that the LiMnPO4/C composites prepared with mixed manganese oxide deliver a superior initial capacity of 153 mAh g-1 at 0.05 C and high rate performance with discharge capacities of 123 mAh g-1 at 1 C and 103 mAh g-1 at 2 C. And the LiMnPO4/C composites synthesized at 600 °C can retain 94% of the initial capacity after 200 cycles at 1 C, revealing a stable cycling stability. Therefore, one-step solid state reaction brings to light the synthesis of high performance LiMnPO4/C cathode materials and is suitable for large scale production.

  5. Enhanced thermal safety and high power performance of carbon-coated LiFePO4 olivine cathode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Dubé, J.; Dallaire, A.; Galoustov, K.; Guerfi, A.; Ramanathan, M.; Benmayza, A.; Prakash, J.; Mauger, A.; Julien, C. M.

    2012-12-01

    The carbon-coated LiFePO4 Li-ion oxide cathode was studied for its electrochemical, thermal, and safety performance. This electrode exhibited a reversible capacity corresponding to more than 89% of the theoretical capacity when cycled between 2.5 and 4.0 V. Cylindrical 18,650 cells with carbon-coated LiFePO4 also showed good capacity retention at higher discharge rates up to 5C rate with 99.3% coulombic efficiency, implying that the carbon coating improves the electronic conductivity. Hybrid Pulse Power Characterization (HPPC) test performed on LiFePO4 18,650 cell indicated the suitability of this carbon-coated LiFePO4 for high power HEV applications. The heat generation during charge and discharge at 0.5C rate, studied using an Isothermal Microcalorimeter (IMC), indicated cell temperature is maintained in near ambient conditions in the absence of external cooling. Thermal studies were also investigated by Differential Scanning Calorimeter (DSC) and Accelerating Rate Calorimeter (ARC), which showed that LiFePO4 is safer, upon thermal and electrochemical abuse, than the commonly used lithium metal oxide cathodes with layered and spinel structures. Safety tests, such as nail penetration and crush test, were performed on LiFePO4 and LiCoO2 cathode based cells, to investigate on the safety hazards of the cells upon severe physical abuse and damage.

  6. Facile synthesis of 3D hierarchical foldaway-lantern-like LiMnPO4 by nanoplate self-assembly, and electrochemical performance for Li-ion batteries.

    PubMed

    Chen, Dezhi; Wei, Wei; Wang, Ruining; Lang, Xiu-Feng; Tian, Yu; Guo, Lin

    2012-08-01

    Olivine-structured LiMnPO(4) with 3D foldaway-lantern-like hierarchical structures have been prepared via a one-step, template-free, solvothermal approach in ethylene glycol. The foldaway-lantern-like LiMnPO(4) microstructures are composed of numerous nanoplates with thickness of about 20 nm. A series of electron microscopy characterization results indicate that the obtained primary LiMnPO(4) nanoplates are single crystalline in nature, growing along the [010] direction in the (100) plane. Time-dependent morphology evolution suggests that ethylene glycol plays dual roles in oriented growth and self-assembly of such unique structures. After carbon coating, the as-prepared LiMnPO(4) cathode demonstrated a flat potential at 4.1 V versus Li/Li(+) with a specific capacity close to 130 mA h g(-1) at 0.1 C, along with excellent cycling stability.

  7. Cycling stability and degradation mechanism of LiMnPO4 based electrodes

    NASA Astrophysics Data System (ADS)

    Moskon, J.; Pivko, M.; Jerman, I.; Tchernychova, E.; Logar, N. Zabukovec; Zorko, M.; Selih, V. S.; Dominko, R.; Gaberscek, M.

    2016-01-01

    Long term stability of LiMnPO4 particles with a crystallite size between ˜20 and 50 nm covered with a dense native carbon coating (14 wt.%) is demonstrated. More than 500 cycles at a rate of C/20, in the potential window of 2.7-4.5 V and a temperature of 55 °C were achieved. During most of the cycling the average capacity decay was less than 0.06% per cycle. After about 500 cycles a sudden capacity drop was observed. Degradation processes in various stages of cycling were thoroughly examined using a range of techniques. Severe surface film formation, manganese dissolution and degradation of LixMnPO4 accompanied by formation of Li4P2O7 were clearly identified. The good long term stability seems to be due to dense, protective carbon coating. Decomposition is most likely initiated at local defects in the microstructure of pyrolytic carbon coating around LiMnPO4 particles. In addition to known degradation mechanisms of LiMnPO4 we observed pronounced gradual amorphization of the olivine crystallites during long-term cycling at 55 °C. Finally, changes in morphology of the carbon black additive after prolonged cycling are reported and commented.

  8. Structural and Electrochemical Characterization of Pure LiFePO 4 and Nanocomposite C- LiFePO 4 Cathodes for Lithium Ion Rechargeable Batteries

    DOE PAGESBeta

    Kumar, Arun; Thomas, R.; Karan, N. K.; Saavedra-Arias, J. J.; Singh, M. K.; Majumder, S. B.; Tomar, M. S.; Katiyar, R. S.

    2009-01-01

    Pure limore » thium iron phosphate ( LiFePO 4 ) and carbon-coated LiFePO 4 (C- LiFePO 4 ) cathode materials were synthesized for Li-ion batteries. Structural and electrochemical properties of these materials were compared. X-ray diffraction revealed orthorhombic olivine structure. Micro-Raman scattering analysis indicates amorphous carbon, and TEM micrographs show carbon coating on LiFePO 4 particles. Ex situ Raman spectrum of C- LiFePO 4 at various stages of charging and discharging showed reversibility upon electrochemical cycling. The cyclic voltammograms of LiFePO 4 and C- LiFePO 4 showed only a pair of peaks corresponding to the anodic and cathodic reactions. The first discharge capacities were 63, 43, and 13 mAh/g for C/5, C/3, and C/2, respectively for LiFePO 4 where as in case of C- LiFePO 4 that were 163, 144, 118, and 70 mAh/g for C/5, C/3, C/2, and 1C, respectively. The capacity retention of pure LiFePO 4 was 69% after 25 cycles where as that of C- LiFePO 4 was around 97% after 50 cycles. These results indicate that the capacity and the rate capability improved significantly upon carbon coating.« less

  9. Hyperfine fields at the Li site in LiFePO(4)-type olivine materials for lithium rechargeable batteries: a (7)Li MAS NMR and SQUID study.

    PubMed

    Tucker, Michael C; Doeff, Marca M; Richardson, Thomas J; Fiñones, Rita; Cairns, Elton J; Reimer, Jeffrey A

    2002-04-17

    The (7)Li NMR isotropic shift for olivine LiMPO(4) (M = Fe, Mn, Co, Ni) is assigned to hyperfine coupling between the (7)Li nucleus and the transition metal unpaired electrons on the basis of the Curie-Weiss temperature dependence of the shift. The hyperfine shift arises from a linear combination of Li-O-M through-bond interactions wherein the unpaired A' electrons contribute a negative shift and the unpaired A' ' electrons contribute a positive shift. The hyperfine coupling constant is determined for each composition.

  10. Cathode performance of LiMnPO 4/C nanocomposites prepared by a combination of spray pyrolysis and wet ball-milling followed by heat treatment

    NASA Astrophysics Data System (ADS)

    Doan, The Nam Long; Taniguchi, Izumi

    LiMnPO 4/C nanocomposites could be prepared by a combination of spray pyrolysis and wet ball-milling followed by heat treatment in the range of spray pyrolysis temperature from 200 to 500 °C. The ordered LiMnPO 4 olivine structure without any impurity phase could be identified by X-ray diffraction analysis for all samples. It could be also confirmed from scanning electron microscopy and transmission electron microscopy observations that the final samples were the LiMnPO 4/C nanocomposites with approximately 100 nm in primary particles size. The LiMnPO 4/C nanocomposite samples were used as cathode active materials for lithium batteries, and the electrochemical tests were carried out for the cell Li|1 M LiPF 6 in EC:DMC = 1:1|LiMnPO 4/C at various charge/discharge rates in three charge modes. As a result, the final sample which was synthesized at 300 °C by spray pyrolysis showed the best electrochemical performance due to the largest specific surface area, the smallest primary particle size and a well distribution of carbon. At galvanostatic charge/discharge rates of 0.05 C, the cell delivered first discharge capacities of 123 and 165 mAh g -1 in correspondence to charge cutoff voltages of 4.4 and 5.0 V, respectively. Furthermore, in a constant current-constant voltage charge mode at 4.4 V, the cells also exhibited initial discharge capacities of 147 mAh g -1 at 0.05 C, 145 mAh g -1 at 0.1 C, 123 mAh g -1 at 1 C and 65 mAh g -1 at 10 C. Moreover, the cells showed fair good cycleability over 100 cycles.

  11. The influence of temperature on a nutty-cake structural material: LiMn1-xFexPO4 composite with LiFePO4 core and carbon outer layer for lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Huo, Zhen-Qing; Cui, Yu-Ting; Wang, Dan; Dong, Yue; Chen, Li

    2014-01-01

    The extremely low electronic conductivity, slow ion diffusion kinetics, and the Jahn-Teller effect of LiMnPO4 limit its electrochemical performance. In this work, a nutty-cake structural C-LiMn1-xFexPO4-LiFePO4 cathode material is synthesized by hydrothermal method and further calcined at different temperatures. The influence of calcination temperature on the electrochemical behavior is investigated by X-ray diffractometer, scanning electron microscope, field-emission high-resolution transmission electron microscope, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and charge-discharge tests. And the performance of C-LiMn1-xFexPO4-LiFePO4 materials has a relationship with its crystal structure. The well-crystallized Sample-600 calcined at 600 °C shows the smallest charge transfer resistance, the largest lithium ion diffusion coefficient (DLi) and the best cycling stability. The discharge capacity of Sample-600 holds around 112 mAh g-1 after the 3rd cycle at 0.1 C rate. The performances improvement of C-LiMn1-xFexPO4-LiFePO4 material can be mainly attributed to the iron diffusion from the LiFePO4 core to the outer LiMnPO4 layer under appropriate calcination temperature.

  12. Olivine-type nanosheets for lithium ion battery cathodes.

    PubMed

    Rui, Xianhong; Zhao, Xiaoxu; Lu, Ziyang; Tan, Huiteng; Sim, Daohao; Hng, Huey Hoon; Yazami, Rachid; Lim, Tuti Mariana; Yan, Qingyu

    2013-06-25

    Olivine-type LiMPO4 (M = Fe, Mn, Co, Ni) has become of great interest as cathodes for next-generation high-power lithium-ion batteries. Nevertheless, this family of compounds suffers from poor electronic conductivities and sluggish lithium diffusion in the [010] direction. Here, we develop a liquid-phase exfoliation approach combined with a solvothermal lithiation process in high-pressure high-temperature (HPHT) supercritical fluids for the fabrication of ultrathin LiMPO4 nanosheets (thickness: 3.7-4.6 nm) with exposed (010) surface facets. Importantly, the HPHT solvothermal lithiation could produce monodisperse nanosheets while the traditional high-temperature calcination, which is necessary for cathode materials based on high-quality crystals, leads the formation of large grains and aggregation of the nanosheets. The as-synthesized nanosheets have features of high contact area with the electrolyte and fast lithium transport (time diffusion constant in at the microsecond level). The estimated diffusion time for Li(+) to diffuse over a [010]-thickness of <5 nm (L) was calculated to be less than 25, 2.5, and 250 μs for LiFePO4, LiMnPO4, and LiCoPO4 nanosheets, respectively, via the equation of t = L(2)/D. These values are about 5 orders of magnitude lower than the corresponding bulk materials. This results in high energy densities and excellent rate capabilities (e.g., 18 kW kg(-1) and 90 Wh kg(-1) at a 80 C rate for LiFePO4 nanosheets).

  13. Electrical conductivity studies of graphene wrapped nanocrystalline LiMnPO4 composite

    NASA Astrophysics Data System (ADS)

    Cheruku, Rajesh; D, Surya Bhaskaram; Govindaraj, G.; Vijayan, Lakshmi

    2015-06-01

    Nanocrystalline LiMnPO4 material was synthesized by template free sucrose assisted hydrothermal method. The material possesses the orthorhombic crystal structure with Pnma, space group having four formula units. The GO was prepared by the hummer's method and it was reduced graphene oxide (rGO) with hydrazine hydrate in the presence of nitrogen atmosphere. LiMnPO4 material was wrapped by the rGO to increase its conductivity. The structural characterization was accomplished through X-ray diffraction, FT-IR and Raman spectroscopy. Morphology was identified by the SEM, Electrical characterization was done through impedance spectroscopy and the results were reported.

  14. Diffusion and possible freezing phases of Li-ions in LiFePO4

    NASA Astrophysics Data System (ADS)

    Yiu, Yuen; Toft-Petersen, Rasmus; Ehlers, Georg; Vaknin, David

    Elastic and inelastic neutron scattering studies of LiFePO4 single crystal reveal new Li-ion diffusion properties relevant to its function as Li-battery materials. In the past decade there has been broad interest in LiFePO4 and its related compounds, largely due to the applications of these materials as cathodes in Li- batteries. This is owing to these materials' high charge-discharge ability and conductivity, both of which are by virtue of the Li-ions' high mobility. In this talk, we present our findings on the temperature and directional dependence of Li-ions' diffusion in LiFePO4. LiFePO4 adopts the olivine structure at room temperature (Space group: Pnma), which contains channels along principal crystalline directions that allow Li-ion motion. Elastic neutron scattering reveals lowering of symmetry from the Pnma structure below room temperature, which can be interpreted as the freezing of Li-ions, and can be subsequently linked to the reported decrease in Li-ion conductivity. Inelastic neutron scattering, in the 35K to 720K temperature range, shows temperature dependence, as well as anisotropy (i.e. along 0K0 versus 00L) of Li-ion diffusion. Ames Laboratory is supported by U.S. DOE, BES, DMSE, under Contract #DE-AC02-07CH11358. Spallation Neutron Source of Oak Ridge National Laboratory is sponsored by U.S. DOE, BES, SUFD.

  15. Electronic Properties of LiFePO4 and Li doped LiFePO4

    SciTech Connect

    Zhuang, G.V.; Allen, J.L.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

    2005-06-28

    The potential use of different iron phosphates as cathodematerials in lithium-ion batteries has recently been investigated.1 Oneof the promising candidates is LiFePO4. This compound has severaladvantages in comparison to the state-of-the-art cathode material incommercial rechargeable lithium batteries. Firstly, it has a hightheoretical capacity (170 mAh/g). Secondly, it occurs as mineraltriphylite in nature and is inexpensive, thermally stable, non-toxic andnon-hygroscopic. However, its low electronic conductivity (~;10-9 S/cm)results in low power capability. There has been intense worldwideresearch activity to find methods to increase the electronic conductivityof LiFePO4, including supervalent ion doping,2 introducingnon-carbonaceous network conduction3 and carbon coating, and theoptimization of the carbon coating on LiFePO4 particle surfaces.4Recently, the Li doped LiFePO4 (Li1+xFe1-xPO4) synthesized at ARL hasyield electronic conductivity increase up to 106.5 We studied electronicstructure of LiFePO4 and Li doped LiFePO4 by synchrotron based soft X-rayemission (XES) and X-ray absorption (XAS) spectroscopies. XAS probes theunoccupied partial density of states, while XES the occupied partialdensity of states. By combining XAS and XES measurements, we obtainedinformation on band gap and orbital character of both LiFePO4 and Lidoped LiFePO4. The occupied and unoccupied oxygen partial density ofstates (DOS) of LiFePO4 and 5 percent Li doped LiFePO4 are presented inFig. 1. Our experimental results clearly indicate that LiFePO4 has wideband gap (~; 4 eV). This value is much larger than what is predicted byDFT calculation. For 5 percent Li doped LiFePO4, a new doping state wascreated closer to the Fermi level, imparting p-type conductivity,consistent with thermopower measurement. Such observation substantiatesthe suggestion that high electronic conductivity in Li1.05Fe0.95 PO4 isdue to available number of charge carriers in the material. Furthermore,Hall effect measurement on Li doped sample confirmed presence of freecharge carriers, which are responsible for the observed electronicconductivity increase in Li doped LiFePO4. There is no evidence that Fe3+valence is created by doping with excessive Li+ in Li1.05Fe0.95PO4, asshown by Fe-edge XAS. (Fig.2) Instead, charge-carrier holes resideprimarily in unoccupied O 2p states, which compensate for the chargedeficiency from Li+ substitution for Fe2+. The increased conductivity inLi1.05Fe0.95PO4 is attributed to the new charge carriers (doped holes)and the strong electron correlation between O 2p and Fe 3dstates.

  16. Temperature Dependence of Aliovalent-vanadium Doping in LiFePO4 Cathodes

    SciTech Connect

    Harrison, Katharine L; Bridges, Craig A; Paranthaman, Mariappan Parans; Idrobo Tapia, Juan C; Manthiram, Arumugam; Goodenough, J. B.; Segre, C; Katsoudas, John; Maroni, V. A.

    2013-01-01

    Vanadium-doped olivine LiFePO4 cathode materials have been synthesized by a novel low-temperature microwave-assisted solvothermal (MW-ST) method at 300 oC. Based on chemical and powder neutron/X-ray diffraction analysis, the compositions of the synthesized materials were found to be LiFe1-3x/2Vx x/2PO4 (0 x 0.2) with the presence of a small number of lithium vacancies charge-compensated by V4+, not Fe3+, leading to an average oxidation state of ~ 3.2+ for vanadium. Heating the pristine 15 % V-doped sample in inert or reducing atmospheres led to a loss of vanadium from the olivine lattice with the concomitant formation of a Li3V2(PO4)3 impurity phase; after phase segregation, a partially V-doped olivine phase remained. For comparison, V-doped samples were also synthesized by conventional ball milling and heating, but only ~ 10 % V could be accommodated in the olivine lattice in agreement with previous studies. The higher degree of doping realized with the MW-ST samples demonstrates the temperature dependence of the aliovalent-vanadium doping in LiFePO4.

  17. Atomic-scale visualization of antisite defects in LiFePO4.

    PubMed

    Chung, Sung-Yoon; Choi, Si-Young; Yamamoto, Takahisa; Ikuhara, Yuichi

    2008-03-28

    We visualize the antisite exchange defects in LiFePO4 crystals with an ordered olivine structure by using annular dark-field scanning transmission electron microscopy (STEM). A recognizable bright contrast is observed in some of the Li columns of STEM images in a sample annealed at a lower temperature, which directly demonstrates the disordered occupations by Fe atoms. Furthermore, such exchange defects appear to be locally aggregated rather than homogeneously dispersed in the lattice, although their overall concentration is fairly low. The present study emphasizes the significance of atomic-level observations for the defect distribution that cannot be predicted by macroscopic analytical methods.

  18. In situ Electrochemical-AFM Study of LiFePO4 Thin Film in Aqueous Electrolyte

    NASA Astrophysics Data System (ADS)

    Wu, Jiaxiong; Cai, Wei; Shang, Guangyi

    2016-04-01

    Lithium-ion (Li-ion) batteries have been widely used in various kinds of electronic devices in our daily life. The use of aqueous electrolyte in Li-ion battery would be an alternative way to develop low cost and environmentally friendly batteries. In this paper, the lithium iron phosphate (LiFePO4) thin film cathode for the aqueous rechargeable Li-ion battery is prepared by radio frequency magnetron sputtering deposition method. The XRD, SEM, and AFM results show that the film is composed of LiFePO4 grains with olivine structure and the average size of 100 nm. Charge-discharge measurements at current density of 10 μAh cm-2 between 0 and 1 V show that the LiFePO4 thin film electrode is able to deliver an initial discharge capacity of 113 mAh g-1. Specially, the morphological changes of the LiFePO4 film electrode during charge and discharge processes were investigated in aqueous environment by in situ EC-AFM, which is combined AFM with chronopotentiometry method. The changes in grain area are measured, and the results show that the size of the grains decreases and increases during the charge and discharge, respectively; the relevant mechanism is discussed.

  19. A polyethylene glycol-assisted carbothermal reduction method to synthesize LiFePO4 using industrial raw materials

    NASA Astrophysics Data System (ADS)

    Fey, George Ting-Kuo; Huang, Kai-Pin; Kao, Hsien-Ming; Li, Wen-Hsien

    2011-03-01

    Olivine LiFePO4 is synthesized by a carbothermal reduction method (CTR) using industrial raw materials with polyethylene glycol (PEG) as a reductive agent and carbon source. A required amount of acetone is added to the starting materials for the ball milling process and the precursor is sintered at 973 K for 8 h to form crystalline phase LiFePO4. The structure and morphology of the LiFePO4/C composite samples have been characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, differential scanning calorimetry and magnetic susceptibility. Electrochemical measurements show that the LiFePO4/C composite cathode delivers an initial discharge capacity of 150 mAh g-1 at a 0.2C-rate between 4.0 and 2.8 V, and almost no capacity loss is observed for up to 50 cycles. Remarkably, the cell can sustain a 30C-rate between 4.6 and 2.0 V, and this rate capability is equivalent to charge or discharge in 2 min. The simple technique, low-cost starting materials, and excellent electrochemical performance make this process easier to commercialize than other synthesized methods.

  20. Aqueous synthesis of LiFePO4 with Fractal Granularity

    NASA Astrophysics Data System (ADS)

    Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P.; Gómez-Romero, Pedro

    2016-06-01

    Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes.

  1. Aqueous synthesis of LiFePO4 with Fractal Granularity

    PubMed Central

    Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P.; Gómez-Romero, Pedro

    2016-01-01

    Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes. PMID:27256504

  2. Aqueous synthesis of LiFePO4 with Fractal Granularity.

    PubMed

    Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P; Gómez-Romero, Pedro

    2016-01-01

    Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes. PMID:27256504

  3. Direct formation of LiFePO4/graphene composite via microwave-assisted polyol process

    NASA Astrophysics Data System (ADS)

    Lim, Jinsub; Gim, Jihyeon; Song, Jinju; Nguyen, Dang Thanh; Kim, Sungjin; Jo, Jeonggeun; Mathew, Vinod; Kim, Jaekook

    2016-02-01

    The present study reports on the direct synthesis of LiFePO4 nanoparticles and graphene nanosheets to form a composite cathode (LFP/GNs) in a one-step microwave-assisted polyol reaction. The polyol reaction induced by microwave irradiation for a few minutes produces nanocrystalline LFP and graphene nanosheets simultaneously from lithium, iron and phosphorus and carbon (5 wt% of graphite oxide) sources, respectively, used as starting precursors. Powder X-ray diffraction (XRD), electron microscopy, and atomic force microscopy (AFM) studies on microwave-reacted sample obtained using just graphite oxide confirms the formation of graphene nanosheets separately. Whereas, electron microscopy studies on the LFP/GNs composite reveals that olivine nanoparticles of average sizes ranging between 5 and 20 nm are well-dispersed on the graphene nanosheets. Electrochemical measurements reveal that the LiFePO4/GNs nanocomposite cathodes registered enhanced discharge capacities (79 and 108 mAh g-1 for the as-prepared and annealed composite cathodes, respectively) at 32 C rates with good capacity retention capabilities. The AC impedance measurements confirm that the enhanced cathode properties of the LFP/GNs nanocomposite are ascribed to the improved electronic conductivity of the graphene nanosheets and the nano-sized particles. The slightly better electrochemical properties of the annealed LFP/GNs are attributed to its higher crystallinity.

  4. Role of Ce and In doping in the performance of LiFePO4 cathode material for Li ion Batteries

    NASA Astrophysics Data System (ADS)

    Mandal, Balaji; Nazri, Mariam; Vaishnava, Prem P.; Naik, Vaman M.; Nazri, Gholam A.; Naik, Ratna

    2012-02-01

    Recently, the olivine LiFePO4 has attracted attention as a promising cathode material for Li ion batteries. However, its poor electronic conductivity is a major challenge for its industrial applications. Different approaches have been taken to address this problem. Here, we report a method of improving its conductivity by doping In and Ce ions at the Fe site. We prepared the samples by sol-gel method followed by annealing at 650 C in Ar (95%) +H2(5%) atmosphere for 5 hrs. XRD and Raman spectroscopy confirm that the olivine structure remains unchanged upon doping with In and Ce up to 5 wt%. XRD analysis shows the values of the lattice parameters increase with doping as the ionic radii of Ce and In ions are larger than that of the Fe^2+ ion. This observation also suggests that both Ce and In ions replace Fe ions and not the Li ions in the material. Upon doping, ionic conductivity was found to increase from 10-9 to 10-4 Ohm-1cm-1. Interestingly, Ce doped LiFePO4 showed a higher conductivity than In doped LiFePO4. SEM measurements show a bigger grain size of ˜300-500 nm in doped LiFePO4 which decreased to ˜50 nm when the materials were synthesized using 0.25M lauric acid as a precursor. The electrochemical characteristics of the doped LiFePO4 along with conductivity and Raman data will be presented.

  5. Effect of synthesizing method on the properties of LiFePO4/C composite for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Yoon, Man-Soon; Islam, Mobinul; Park, Young Min; Ur, Soon-Chul

    2013-03-01

    Olivine-type LiFePO4/C cathode materials are fabricated with FePO4 powders that are pre-synthesized by two different processes from iron chloride solution. Process I is a modified precipitation method which is implemented by the pH control of a solution using NH4OH to form FePO4 precipitates at room temperature. Process II is a conventional precipitation method, of which H3PO4 (85%) solution is gradually added to a FeCl3 solution during the process to maintain a designated mole ratio. The solution is subsequently aged at 90°C in a water bath until FePO4 precipitates appear. In order to synthesize LiFePO4/C composites, each batch of FePO4 powders is then mixed with pre-milled lithium carbonate and glucose (8 wt. %) as a carbon source in a ball-mill. The structural characteristics of both LiFePO4/C composites fabricated using iron phospates from two different routes have been examined employing XRD and SEM. The modified precipitation process is considered to be a relatively simple and effective process for the preparation of LiFePO4/C composites owing to their excellent electrochemical properties and rate capabilities.

  6. Solid Solution Phases in the Olivine-Type LiMnPO4/MnPO4 System

    SciTech Connect

    Chen, Guoying; Richardson, Thomas J.

    2009-04-07

    Nonstoichiometry is reported in the LiMnPO{sub 4}/MnPO{sub 4} system for the first time. As lithium is removed from crystalline LiMnPO{sub 4} by chemical or electrochemical methods, the resulting two phase mixture consists of stoichiometric LiMnPO{sub 4} and a delithiated phase, Li{sub y}MnPO{sub 4}, whose lattice parameters depend upon the global extent of delithiation and on the crystalline domain size of the delithiated phase. This behavior is reproduced during electrochemical insertion of lithium. Again, no evidence for nonstoichiometry was found in the vicinity of LiMnPO{sub 4}. Attempts to create single phase solid solutions by heating mixtures of the two phases failed due to the thermal instability of Li{sub y}MnPO{sub 4}.

  7. Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes

    PubMed Central

    2016-01-01

    LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g–1) and working voltage (4.1 V vs Li+/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g–1 at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g–1. The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times. PMID:26799094

  8. Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes.

    PubMed

    Chen, Lin; Dilena, Enrico; Paolella, Andrea; Bertoni, Giovanni; Ansaldo, Alberto; Colombo, Massimo; Marras, Sergio; Scrosati, Bruno; Manna, Liberato; Monaco, Simone

    2016-02-17

    LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g(-1)) and working voltage (4.1 V vs Li(+)/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g(-1) at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g(-1). The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times.

  9. Amphiphilic carbonaceous material-intervened solvothermal synthesis of LiFePO4

    NASA Astrophysics Data System (ADS)

    Chen, Ming-ming; Ma, Qian-qian; Wang, Cheng-yang; Sun, Xin; Wang, Li-qun; Zhang, Cui

    2014-10-01

    LiFePO4 samples with preferred facets on the ac plane were prepared by the solvothermal method with or without well-dispersed amphiphilic carbonaceous material (ACM). The effects of ACM on the particle morphology, crystal orientation and electrochemical reactivity of the prepared LiFePO4 nanoparticles were investigated in detail. ACM serves a dual purpose. One purpose is facilitating the plate-like morphologies of LiFePO4 nanoparticles parallel to the bPnma axis by decreasing the surface energy of (010) facets of newly created LiFePO4 nuclei. The other purpose is suppressing crystal growth along the [010] direction by adhering onto the (010) surface of LiFePO4 nanoplates. Furthermore, ACM coating was performed and optimized using a carbon coating precursor. The electrochemical properties of the prepared LiFePO4 particles were characterized by cyclic voltammetry (CV) and galvanostatic charge-discharge cycling tests. After the optimized coating of ACM, the ACM-intervened LiFePO4 composite was observed to deliver discharge capacities of 151.3 mAh g-1 at 1C and 132.2 mAh g-1 at 10C. Even after 1000 cycles at a high rate of 10C, the LiFePO4 cathode could maintain 80% of its initial capacity.

  10. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X. S.

    2013-12-01

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg2+ doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg2+ doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li+ diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg2+ doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of ``cushion'' as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co

  11. Comparison of LiFePO4 from different sources

    SciTech Connect

    Striebel, Kathryn; Shim, Joongpyo; Srinivasan, Venkat; Newman, John

    2003-11-25

    The lithium iron phosphate chemistry is plagued by the poor conductivity and slow lithium diffusion in the solid phase. In order to alleviate these problems, various research groups have adopted different strategies including decreasing the particle sizes, increasing the carbon content, and adding dopants. In this study we obtained LiFePO4 electrodes from six different sources and used a combined model-experimental approach to compare the performance. Samples ranged from one with no carbon coating to one with 15 percent coating. In addition, particle sizes varied by as much as a order of magnitude between samples. The study detailed in this manuscript allows us to provide insight into the relative importance of the conductivity of the samples compared to the particle size, the impact of dopant on performance and ideas for making materials in order to maximize the power capability of this chemistry.

  12. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries.

    PubMed

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X S

    2014-01-21

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg(2+) doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg(2+) doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li(+) diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg(2+) doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of "cushion" as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.

  13. Comparison of LiMnPO4 made by Combustion and Hydrothermal Syntheses

    SciTech Connect

    Chen, Jiajun; Doeff, Marca M.; Wang, Ruigang

    2008-05-15

    Among the olivine-structured metal phosphate family, LiMnPO{sub 4} exhibits a high discharge potential (4V), which is still compatible with common electrolytes, making it interesting for use in the next generation of Li ion batteries. The extremely low electronic conductivity of this material severely limits its electrochemical performance, however. One strategy to overcome this limitation is to make LiMnPO{sub 4} nanoparticulate to decrease the diffusion distance. Another is to add a carbon or other conductive coating in intimate contact with the nanoparticles of the main phase, as is commonly done with LiFePO{sub 4}. The electrochemical performance of LiFePO{sub 4} is highly dependent on the quality of the carbon coatings on the particles [1-2], among other variables. Combustion synthesis allows the co-synthesis of nanoparticles coated with carbon in one step. Hydrothermal synthesis is used industrially to make LiFePO{sub 4} cathode materials [3] and affords a good deal of control over purity, crystallinity, and particle size. A wide range of olivine-structured materials has been successfully prepared by this technique [4], including LiMnPO{sub 4} in this study. In this paper, we report on the new synthesis of nano-LiMnPO{sub 4} by a combustion method. The purity is dependent upon the conditions used for synthesis, including the type of fuel and precursors that are chosen. The fuel to nitrate ratio influences the combustion temperature, which determines the type and amount of carbon found in the LiMnPO{sub 4} composites. This can further be modified by use of carbon structural modifiers added during a subsequent (optional) calcination step. Figure 1 shows a transmission electron microscopy (TEM) image of the spherical nano-sized LiMnPO{sub 4} particles typically formed by combustion synthesis. The average particle size is around 30 nm, in agreement with values obtained by the Rietveld refinement of XRD patterns. The small size of the particles cause the peak

  14. Comparison of LiMnPO4 made by Combustion and Hydrothermal Syntheses

    SciTech Connect

    Chen, Jiajun; Doeff, Marca M.; Wang, Ruigang

    2008-10-12

    Among the olivine-structured metal phosphate family, LiMnPO{sub 4} exhibits a high discharge potential (4V), which is still compatible with common electrolytes, making it interesting for use in the next generation of Li ion batteries. The extremely low electronic conductivity of this material severely limits its electrochemical performance, however. One strategy to overcome this limitation is to make LiMnPO{sub 4} nanoparticulate to decrease the diffusion distance. Another is to add a carbon or other conductive coating in intimate contact with the nanoparticles of the main phase, as is commonly done with LiFePO{sub 4}. The electrochemical performance of LiFePO{sub 4} is highly dependent on the quality of the carbon coatings on the particles, among other variables. Combustion synthesis allows the co-synthesis of nanoparticles coated with carbon in one step. Hydrothermal synthesis is used industrially to make LiFePO{sub 4} cathode materials and affords a good deal of control over purity, crystallinity, and particle size. A wide range of olivine-structured materials has been successfully prepared by this technique, including LiMnPO{sub 4} in this study. In this paper, we report on the new synthesis of nano-LiMnPO{sub 4} by a combustion method. The purity is dependent upon the conditions used for synthesis, including the type of fuel and precursors that are chosen. The fuel to nitrate ratio influences the combustion temperature, which determines the type and amount of carbon found in the LiMnPO{sub 4} composites. This can further be modified by use of carbon structural modifiers added during a subsequent (optional) calcination step. Figure 1 shows a transmission electron microscopy (TEM) image of the spherical nano-sized LiMnPO{sub 4} particles typically formed by combustion synthesis. The average particle size is around 30 nm, in agreement with values obtained by the Rietveld refinement of XRD patterns. The small size of the particles cause the peak broadening evident

  15. Atomic structural and electrochemical impact of Fe substitution on nano porous LiMnPO4

    NASA Astrophysics Data System (ADS)

    Seo, Inseok; Senthilkumar, B.; Kim, Kwang-Ho; Kim, Jae-Kwang; Kim, Youngsik; Ahn, Jou-Hyeon

    2016-07-01

    The atomic structural and electrochemical properties of Fe substituted nano porous LiMn1-xFexPO4 (x = 0-0.8) composites are investigated and compared. X-ray scattering method is used for atomic structural investigation. Rietveld refinement shows that all Fe substituted composites have the same olivine structure (Pnma) with lithium occupying octahedral 4a sites, Fe2+ replacing Mn2+ at the octahedral 4c sites. The a, b, c parameters and cell volume decrease with the addition of Fe2+. When the nano porous LiMn1-xFexPO4 composites are evaluated as cathode materials in lithium cells at room temperature, x = 0.6, and 0.8 resulted in the best overall electrochemical performance, exhibiting stable cycling and high discharge capacities of 149 and 154 mA h g-1, respectively. The composites with above x = 0.4 show a fast lithium ions transfer with high electronic conductivity because Fe transition metal substitution reduce the partly occupation of Mn in the M1 (LiO6) sites and thereby Mn block the lithium ion diffusion pathway. We here firstly find the antisite defect in the high Mn content in porous LiMn1-xFexPO4 composites.

  16. Dispersion, agglomeration, and gelation of LiFePO4 in water-based slurry

    NASA Astrophysics Data System (ADS)

    Tsai, Feng-Yen; Jhang, Jia-Hao; Hsieh, Han-Wei; Li, Chia-Chen

    2016-04-01

    The gelation of commercially available lithium iron phosphate (LiFePO4) in water-based slurry and its corresponding mechanism are studied. Based on surface chemistry analyses using zeta potential measurements and Fourier transform infrared spectroscopy, it is found that the key factor that causes LiFePO4 gelation in the aqueous slurry is the quality of the surface carbon coating on powder. When the surface carbon exhibits functional derivatives, such as carboxyl, hydroxyl, and carbonyl polar functional groups, LiFePO4 tends to form a three-dimensional, gel-like structure via hydrogen bonding. Moreover, the presence of the derivatives reduces the amount of conduction-favorable sp2-bonded carbon to LiFePO4, resulting in an electric resistance increase of the as-prepared electrode and the deterioration of the specific capacity of the as-constructed cell.

  17. Anode property of carbon coated LiFePO4 nanocrystals

    NASA Astrophysics Data System (ADS)

    Ni, Jiangfeng; Jiang, Jiaxing; Savilov, S. V.; Aldoshin, S. M.

    2016-10-01

    Nanostructured LiFePO4 is appealing cathode material for rechargeable lithium batteries. Herein, however, we report the intriguing anode properties of carbon coated LiFePO4 nanocrystals. In the potential range of 0-3.0 V, the LiFePO4 nanocrystal electrodes afford high reversible capacity of 373 mAhg-1 at a current rate of 0.05 Ag-1 and retains 239 mAhg-1 at a much higher rate of 1.25 Ag-1. In addition, it is capable of sustaining 1000 cycles at 1.25 Ag-1 without any capacity fading. Such superior properties indicate that nanostructured LiFePO4 could also be promising anode for rechargeable battery applications.

  18. The source of first-cycle capacity loss in LiFePO 4

    NASA Astrophysics Data System (ADS)

    Andersson, A. S.; Thomas, J. O.

    The electrochemical extraction of lithium from solid-state synthesised LiFePO 4 has been studied by neutron powder diffraction. A "coffee-bag" type cell of configuration has been charged to 4.1 V, dismantled in a glovebox, and the composite cathode powder sample scraped from the current collector. Two-phase Rietveld refinement gave a triphylite (LiFePO 4) to heterosite (FePO 4) phase-ratio of 18:82. In the absence of significant absorption effects, this ratio is a true representation of the conversion of LiFePO 4 to FePO 4. Possible mechanisms for lithium extraction/insertion during the first-cycle are discussed.

  19. Enhanced rate performance of multiwalled carbon nanotube encrusted olivine type composite cathode material using polyol technique

    NASA Astrophysics Data System (ADS)

    Muruganantham, R.; Sivakumar, M.; Subadevi, R.

    2015-12-01

    Olivine type multi-walled carbon nanotube encrusted LiFePO4/C composites have been prepared using economic and energy efficient simple polyol technique without any subsequent heat treatment. The prepared material has an olivine type orthorhombic phase. Also, the iron oxidation state is 2+, which is identified by X-ray diffraction and X-ray photoelectron spectroscopy. It is possible to attain the discharge capacity almost close to theoretical capacity of LiFePO4 as in high temperature methods with ∼100% coulombic efficiency. The specific surface area has been increased upon encrusting multi walled carbon nano tube on LiFePO4/C, which results in enhanced reversible capacity upto 166 mAh g-1 at C/10. Also, it exhibits 89 mAh g-1 even at 30 C rate. This is due to the formation of conductive networks by carbon nanotube, and excellent attachment of LiFePO4/C composite particles on multi-walled carbon nanotube, which induced the kinetics during intercalation/deintercalation process. Multi-walled carbon nanotube acts as the electro-conductive filler on the LiFePO4 surface. The direct addition of MWCNT would result better performances than blending the MWCNT with LiFePO4/C.

  20. Unlocking the energy capabilities of micron-sized LiFePO4

    NASA Astrophysics Data System (ADS)

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-08-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a `carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

  1. Unlocking the energy capabilities of micron-sized LiFePO4

    PubMed Central

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-01-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a ‘carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations. PMID:26235395

  2. Unlocking the energy capabilities of micron-sized LiFePO4.

    PubMed

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G; Peng, Zhangquan

    2015-08-03

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a 'carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

  3. Thermal Stability and Phase Transformation of Electrochemically Charged/Discharged LiMnPO4 Cathode for Li-Ion Battery

    SciTech Connect

    Choi, Daiwon; Xiao, Jie; Choi, Young Joon; Hardy, John S.; Vijayakumar, M.; Bhuvaneswari, M. S.; Liu, Jun; Xu, Wu; Wang, Wei; Yang, Zhenguo; Graff, Gordon L.; Zhang, Jiguang

    2011-11-01

    Electrochemically active LiMnPO4 nanoplate at lithiated/delithiated state were subjected to thermal stability and phase transformation evaluate for safety as a cathode material for Li-ion battery. The phase transformation and oxygen evolution temperature on the delithiated MnPO4 were characterized using in-situ hot-stage X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), thermogravimetric - differential scanning calorimetry - mass spectroscopy (TGA-DSC-MS), transmission electron microscopy and scanning electron microscopy (SEM) - energy dispersive X-ray analysis (EDAX).

  4. Coating the Conductivity Materials to Improving the Electrochemical Properties of LiFePO4

    NASA Astrophysics Data System (ADS)

    Wang, Wan Lin; Jin, En Mei; Gu, Hal-Bon

    2013-03-01

    LiFePO4 cathode materials were prepared by a solid-state method followed by one-step heat treatment. To improve the electrochemical properties of the LiFePO4, acetylene black (AB), citric acid (CA), and pyrene are added as carbon source, respectively. The cyclic voltammetry (CV), AC impedance and galvanostatic charge/discharge testing results showed that using the LiFePO4-C composite such as the AB carbon source exhibits higher discharge capacity and stability than the other composite. Synthesized LiFePO4-C/Li cells (with AB) showed that initial discharge capacity was 140.65 mA h g-1 and at the 2nd cycle were 145.87 mA h g-1, respectively. Morphology and electrochemical performance of the LiFePO4 cathode materials were investigated. Furthermore, the cell was subjected to current density studies (0.1 mA cm-2) that suggested excellent capacity retention of the cell at 25°C.

  5. Electrical relaxation studies of olivine type nanocrystalline LiMPO4 (M=Ni, Mn and Co) materials

    NASA Astrophysics Data System (ADS)

    Cheruku, Rajesh; Kruthika, G.; Govindaraj, G.; Vijayan, Lakshmi

    2015-11-01

    The olivine type LiMPO4 (M=Ni, Mn and Co) materials were synthesized by solution combustion technique using glycine as fuel. The structural characterizations were explored to confirm the phase formation of materials. The scanning electron microscope was used to identify the morphology of olivine materials. The local structure and chemical bonding between MO6 octahedral and (PO4)3- tetrahedral groups were probed by Raman spectroscopy. Grain and grain boundaries were contributed for ion relaxation and dc conduction in olivine materials. Two orders of enhancement in ionic conductivity was observed in these olivine materials than the reported value. Among all the explored olivine samples, LiMnPO4 showed highest enhancement in conductivity due to weak Li-O bonding and largest unit cell volume.

  6. Synthesis and characterization of LiFePO4 cathode preparation by low temperature method

    NASA Astrophysics Data System (ADS)

    Rajesh, Desapogu; Srinivas Naik, V.; Sunandana, C. S.

    2015-05-01

    We review in detail the physics and technology of the novel material LiFePO4, a potential cathode material for Li-ion batteries. In the present work, nano crystalline LiFePO4 film has been synthesized in both powder and thin film forms from a non-aqueous sol-gel synthesis route based on oxalates of Li and Fe (II). Ferrous oxalate has been synthesized indigenously using a ferrous sulphate based chemical reaction and characterized. Nano powders and thin films of LiFePO4 have been fabricated and coated on stainless steel substrates with the aim of device development in future. The material has been characterized extensively by XRD for crystal structure, FESEM for microstructure, EDS for elemental analysis and FTIR for the internal modes of phosphate ion. Fe3+ impurity characterization has been done by using ESR.

  7. Carbon Surface Layers on a High-Rate LiFePO4

    SciTech Connect

    Gabrisch, Heike; Wilcox, James D.; Doeff, Marca M.

    2005-09-06

    Transmission electron microscopy (TEM) was used to image particles of a high-rate LiFePO4 sample containing a small amount of in situ carbon. The particle morphology is highly irregular, with a wide size distribution. Nevertheless, coatings, varying from about 5-10 nm in thickness, could readily be detected on surfaces of particles as well as on edges of agglomerates. Elemental mapping using Energy Filtered TEM (EFTEM) indicates that these very thin surface layers are composed of carbon. These observations have important implications for the design of high-rate LiFePO4 materials in which, ideally, a minimal amount of carbon coating is used.

  8. TEM Studies of Carbon Coated LiFePO4 after Charge DischargeCycling

    SciTech Connect

    Gabrisch, H.; Wilcox, J.; Doeff, M.

    2006-11-30

    Carbon coating has proven to be a successful approach toimprove the rate capability of LiFePO4 used in rechargeable Li-ionbatteries. Investigations of the microstructure of carbon coated LiFePO4after charge discharge cycling shows that the carbon surface layerremains intact over 100 cycles. We find micro cracks in the cycledmaterial that extend parallel to low indexed lattice planes. Ourobservations differ from observations made by other authors. However thedifferences between the orientations of crack surfaces in both studiescan be reconciled considering the location of weak bonds in the unit celland specimen geometry as well as elastic stress fields ofdislocation.

  9. Conductive surface modification of LiFePO4 with nitrogen doped carbon layers for lithium-ion batteries

    SciTech Connect

    Yoon, Sukeun; Liao, Chen; Sun, Xiao-Guang; Bridges, Craig A; Unocic, Raymond R; Nanda, Jagjit; Dai, Sheng; Paranthaman, Mariappan Parans

    2012-01-01

    The LiFePO4 rod surface modified with nitrogen doped carbon layer has been prepared using hydrothermal processing followed by post-annealing in the presence of an ionic liquid. The coated LiFePO4 rod exhibits good capacity retention and high rate capability as the nitrogen doped carbon improves conductivity and prevents aggregation of the rod during cycling.

  10. LiFePO4 - 3D carbon nanofiber composites as cathode materials for Li-ions batteries

    NASA Astrophysics Data System (ADS)

    Dimesso, L.; Spanheimer, C.; Jaegermann, W.; Zhang, Y.; Yarin, A. L.

    2012-03-01

    The characterization of carbon nanofiber 3D nonwovens, prepared by electrospinning process, coated with olivine structured lithium iron phosphate is reported. The LiFePO4 as cathode material for lithium ion batteries was prepared by a Pechini-assisted reversed polyol process. The coating has been successfully performed on carbon nanofiber 3D nonwovens by soaking in aqueous solution containing lithium, iron salts and phosphates at 70 °C for 2-4 h. After drying-out, the composites were annealed at 600 °C for 5 h under nitrogen. The surface investigation of the prepared composites showed a uniform coating of the carbon nonwoven nanofibers as well as the formation of cauliflower-like crystalline structures which are uniformly distributed all over the surface area of the carbon nanofibers. The electrochemical measurements on the composites showed good performances delivering a discharge specific capacity of 156 mAhg- 1 at a discharging rate of C/25 and 152 mAhg- 1 at a discharging rate of C/10 at room temperature.

  11. Porous LiFePO4/C microspheres as high-power cathode materials for lithium ion batteries.

    PubMed

    Sun, Bing; Wang, Ying; Wang, Bei; Kim, Hyun-Soo; Kim, Woo-Seong; Wang, Guoxiu

    2013-05-01

    Porous LiFePO4/C microspheres were synthesized by a novel hydrothermal reaction combined with high-temperature calcinations. The morphology of the prepared material was investigated by field-emission scanning electron microscopy. Porous microspheres with diameters around 1-3 microm were obtained, which consisting of primary LiFePO4 nanoparticles. The electrochemical performances of the as-prepared LiFePO4 microspheres were evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge cycling. The carbon coated LiFePO4 microspheres showed lower polarization, higher rate capability, and better cycling stability than that of pristine LiFePO4 microspheres, indicating the potential application as the cathode material for high-power lithium ion batteries.

  12. Improved battery performance using Pd nanoparticles synthesized on the surface of LiFePO4/C by ultrasound irradiation

    NASA Astrophysics Data System (ADS)

    Saliman, Muhammad Ali; Okawa, Hirokazu; Takai, Misaki; Ono, Yuki; Kato, Takahiro; Sugawara, Katsuyasu; Sato, Mineo

    2016-07-01

    LiFePO4 has been attracting interest as a cathode material for Li-ion batteries due to its high energy density, low cost, and eco-friendliness. The electrochemical performance of LiFePO4 is limited because it exhibits low Li-ion diffusivity and low electronic conductivity. Numerous solutions have been considered, such as carbon coating, which is widely known to improve the electronic conductivity of LiFePO4. The deposition of metal nanoparticles (NPs) on the surface of carbon-coated LiFePO4 further enhances the electronic conductivity. In this study, we deposited Pd NPs onto the surface of LiFePO4/C and investigated the resulting electrochemical performance. Sonochemical synthesis was used to prepare the metal NPs; the procedure did not require any surfactants and the reaction was rapid.

  13. Hierarchical LiFePO4 with a controllable growth of the (010) facet for lithium-ion batteries

    PubMed Central

    Guo, Binbin; Ruan, Hongcheng; Zheng, Cheng; Fei, Hailong; Wei, Mingdeng

    2013-01-01

    Hierarchically structured LiFePO4 was successfully synthesized by ionic liquid solvothermal method. These hierarchically structured LiFePO4 samples were constructed from nanostructured platelets with their (010) facets mainly exposed. To the best of our knowledge, facet control of a hierarchical LiFePO4 crystal has not been reported yet. Based on a series of experimental results, a tentative mechanism for the formation of these hierarchical structures was proposed. After these hierarchically structured LiFePO4 samples were coated with a thin carbon layer and used as cathode materials for lithium-ion batteries, they exhibited excellent high-rate discharge capability and cycling stability. For instance, a capacity of 95% can be maintained for the LiFePO4 sample at a rate as high as 20 C, even after 1000 cycles. PMID:24071818

  14. Hydrothermal preparation of LiFePO 4 nanocrystals mediated by organic acid

    NASA Astrophysics Data System (ADS)

    Ni, Jiangfeng; Morishita, Masanori; Kawabe, Yoshiteru; Watada, Masaharu; Takeichi, Nobuhiko; Sakai, Tetsuo

    Well-crystallized LiFePO 4 nanoparticles have been directly synthesized in a short time via hydrothermal process in the presence of organic acid, e.g. citric acid or ascorbic acid. These acid-mediated LiFePO 4 products exhibit a phase-pure and nanocrystal nature with size about 50-100 nm. Two critical roles that the organic acid mediator plays in hydrothermal process are recognized and a rational mechanism is explored. After a post carbon-coating treatment at 600 °C for 1 h, these mediated LiFePO 4 materials show a high electrochemical activity in terms of reversible capacity, cycling stability and rate capability. Particularly, LiFePO 4 mediated by ascorbic acid can deliver a capacity of 162 mAh g -1 at 0.1 C, 154 mAh g -1 at 1 C, and 122 mAh g -1 at 5 C. The crystalline structure, particle morphology, and surface microstructure were characterized by high-energy synchrotron X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), and Raman spectroscopy, respectively. And the electrochemical properties were thoroughly investigated by galvanostatic test and electrochemical impedance spectroscopy (EIS).

  15. Can Vanadium Be Substituted into LiFePO4

    SciTech Connect

    Omenya F.; Nam K.; Chernova N.A.; Upreti S.; Zavalij P.Y.; Nam K.-W.; Yang X.-Q.; Whittingham M.S.

    2011-11-08

    Vanadium is shown to substitute for iron in the olivine LiFePO{sub 4} up to at least 10 mol %, when the synthesis is carried out at 550 C. In the solid solution LiFe{sub 1-3y/2}V{sub y}PO{sub 4}, the a and b lattice parameters and cell volume decrease with increasing vanadium content, while the c lattice parameter increases slightly. However, when the synthesis is performed at 650 C, a NASICON phase, Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}, is also formed, showing that solid solution is a function of the synthesis temperature. X-ray absorption near-edge structure indicates vanadium is in the 3+ oxidation state and in an octahedral environment. Magnetic studies reveal a shift of the antiferromagnetic ordering transition toward lower temperatures with increasing vanadium substitution, confirming solid solution formation. The addition of vanadium enhances the electrochemical performance of the materials especially at high current densities.

  16. Microbundles of carbon nanostructures as binder free highly conductive matrix for LiFePO4 battery cathode

    NASA Astrophysics Data System (ADS)

    Lalia, Boor Singh; Shah, Tushar; Hashaikeh, Raed

    2015-03-01

    Microbundles of carbon nanostructures (CNS) have been used to fabricate binder-free LiFePO4 electrodes. The inherent ability of CNS to form a nano-porous structure after the reassembly of CNS dispersion from solution to film-forming state is used to encapsulate the LiFePO4 particles. The LiFePO4/CNS electrode shows high electrical conductivity of 9.1 S cm-1 compared to 0.4 S cm -1 for conventional LiFePO4/carbon electrodes. LiFePO4/CNS flexible electrodes shows specific discharge capacity of 56 mAh g-1, 41 mAh g-1 and 37 mAh g-1 at 1C, 3C and 5C rates respectively. These specific discharge capacities are higher than that of conventional LiFePO4/carbon electrodes i.e. 40 mAh g-1, 13 mAh g-1 and 0.01 mAh g-1 at 1C, 3C and 5C rates respectively. Improvements in the specific discharge capacity at high C-rate is attributed to highly conductive pathways between the CNS and LiFePO4 particles, which assist fast transport of electrons at the electrode/CNS interfaces and between the electrode particles for rapid electrochemical reactions.

  17. Single-crystalline LiFePO4 nanosheets for high-rate Li-ion batteries.

    PubMed

    Zhao, Yu; Peng, Lele; Liu, Borui; Yu, Guihua

    2014-05-14

    The lithiation/delithiation in LiFePO4 is highly anisotropic with lithium-ion diffusion being mainly confined to channels along the b-axis. Controlling the orientation of LiFePO4 crystals therefore plays an important role for efficient mass transport within this material. We report here the preparation of single crystalline LiFePO4 nanosheets with a large percentage of highly oriented {010} facets, which provide the highest pore density for lithium-ion insertion/extraction. The LiFePO4 nanosheets show a high specific capacity at low charge/discharge rates and retain significant capacities at high C-rates, which may benefit the development of lithium batteries with both favorable energy and power density.

  18. Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation.

    PubMed

    Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K; Dell'anna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C; Richardson, Thomas J; Kostecki, Robert; Cabana, Jordi

    2013-05-14

    The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

  19. Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation

    PubMed Central

    Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K.; Dell’Anna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C.; Richardson, Thomas J.; Kostecki, Robert; Cabana, Jordi

    2013-01-01

    The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

  20. Optimized Operating Range for Large-Format LiFePO4/Graphite Batteries

    SciTech Connect

    Jiang, Jiuchun; Shi, Wei; Zheng, Jianming; Zuo, Pengjian; Xiao, Jie; Chen, Xilin; Xu, Wu; Zhang, Jiguang

    2014-06-01

    e investigated the long-term cycling performance of large format 20Ah LiFePO4/graphite batteries when they are cycled in various state-of-charge (SOC) ranges. It is found that batteries cycled in the medium SOC range (ca. 20~80% SOC) exhibit superior cycling stability than batteries cycled at both ends (0-20% or 80-100%) of the SOC even though the capcity utilized in the medium SOC range is three times as large as those cycled at both ends of the SOC. Several non-destructive techniques, including a voltage interruption approach, model-based parameter identification, electrode impedance spectra analysis, ΔQ/ΔV analysis, and entropy change test, were used to investigate the performance of LiFePO4/graphite batteries within different SOC ranges. The results reveal that batteries at the ends of SOC exhibit much higher polarization impedance than those at the medium SOC range. These results can be attributed to the significant structural change of cathode and anode materials as revealed by the large entropy change within these ranges. The direct correlation between the polarization impedance and the cycle life of the batteries provides an effective methodology for battery management systems to control and prolong the cycle life of LiFePO4/graphite and other batteries.

  1. A chemically activated graphene-encapsulated LiFePO4 composite for high-performance lithium ion batteries.

    PubMed

    Ha, Jeonghyun; Park, Seung-Keun; Yu, Seung-Ho; Jin, Aihua; Jang, Byungchul; Bong, Sungyool; Kim, In; Sung, Yung-Eun; Piao, Yuanzhe

    2013-09-21

    A composite of modified graphene and LiFePO4 has been developed to improve the speed of charging-discharging and the cycling stability of lithium ion batteries using LiFePO4 as a cathode material. Chemically activated graphene (CA-graphene) has been successfully synthesized via activation by KOH. The as-prepared CA-graphene was mixed with LiFePO4 to prepare the composite. Microscopic observation and nitrogen sorption analysis have revealed the surface morphologies of CA-graphene and the CA-graphene/LiFePO4 composite. Electrochemical properties have also been investigated after assembling coin cells with the CA-graphene/LiFePO4 composite as a cathode active material. Interestingly, the CA-graphene/LiFePO4 composite has exhibited better electrochemical properties than the conventional graphene/LiFePO4 composite as well as bare LiFePO4, including exceptional speed of charging-discharging and excellent cycle stability. That is because the CA-graphene in the composite provides abundant porous channels for the diffusion of lithium ions. Moreover, it acts as a conducting network for easy charge transfer and as a divider, preventing the aggregation of LiFePO4 particles. Owing to these properties of CA-graphene, LiFePO4 could demonstrate enhanced and stably long-lasting electrochemical performance.

  2. Enhanced electrochemical performance in LiFePO4/graphene nanocomposite cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Dhindsa, Kulwinder; Mandal, B.; Lin, M. W.; Nazri, M.; Vaishnava, P.; Naik, V.; Nazri, G. A.; Naik, R.; Zhou, Z. X.

    2012-02-01

    We synthesized LiFePO4/graphene nano-composite employing a sol-gel method, where graphene oxide solution was added to the LiFePO4 precursors during the synthesis. Electrical measurement reveals that the addition of 10% graphene (by weight) to LiFePO4 increases its conductivity by 5 orders of magnitude. SEM images of the composite show that the material consists of LiFePO4 nanoparticles (with a mean particle size ˜ 50 nm) homogeneously mixed with graphene sheets; the latter provides a three-dimensional conducting network for Li+ ion and electron transport. A large specific capacity of 170 mAh/g was observed at a discharge rate of C/2. To further increase the conductivity and inhibit particle size growth of LiFePO4 (thus to increase the rate capacity), we coated the nanoparticles with a thin carbon layer by adding 0.25M lauric acid as precursor in addition to graphene oxide during the synthesis. The respective roles of graphene and lauric-acid-induced carbon coating in the specific capacity and charge-discharge rate of the LiFePO4 cathode material will be discussed.

  3. The influence of reduced graphene oxide on electrical conductivity of LiFePO4-based composite as cathode material

    NASA Astrophysics Data System (ADS)

    Arifin, Muhammad; Aimon, Akfiny Hasdi; Winata, Toto; Abdullah, Mikrajuddin; Iskandar, Ferry

    2016-02-01

    LiFePO4 is fascinating cathode active materials for Li-ion batteries application because of their high electrochemical performance such as a stable voltage at 3.45 V and high specific capacity at 170 mAh.g-1. However, their low intrinsic electronic conductivity and low ionic diffusion are still the hindrance for their further application on Li-ion batteries. Therefore, the efforts to improve their conductivity are very important to elevate their prospecting application as cathode materials. Herein, we reported preparation of additional of reduced Graphene Oxide (rGO) into LiFePO4-based composite via hydrothermal method and the influence of rGO on electrical conductivity of LiFePO4-based composite by varying mass of rGO in composition. Vibration of LiFePO4-based composite was detected on Fourier Transform Infrared Spectroscopy (FTIR) spectra, while single phase of LiFePO4 nanocrystal was observed on X-Ray Diffraction (XRD) pattern, it furthermore, Scanning Electron Microscopy (SEM) images showed that rGO was distributed around LiFePO4-based composite. Finally, the 4-point probe measurement result confirmed that the optimum electrical conductivity is in additional 2 wt% rGO for range 1 to 2 wt% rGO.

  4. A high performance hybrid battery based on aluminum anode and LiFePO4 cathode

    DOE PAGESBeta

    Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Bridges, Craig A.; Paranthaman, Mariappan Parans; Dai, Sheng; Brown, Gilbert M.

    2015-12-07

    A unique battery hybrid utilizes an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g-1 at a current rate of C/5. It also shows good rate capability and cycling performance.

  5. A high performance hybrid battery based on aluminum anode and LiFePO4 cathode.

    PubMed

    Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Fang, Youxing; Bridges, Craig A; Paranthaman, M Parans; Dai, Sheng; Brown, Gilbert M

    2016-01-28

    A novel hybrid battery utilizing an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) (EMImCl-AlCl3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. The hybrid ion battery delivers an initial high capacity of 160 mA h g(-1) at a current rate of C/5. It also shows good rate capability and cycling performance.

  6. Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

    PubMed

    Paolella, Andrea; Turner, Stuart; Bertoni, Giovanni; Hovington, Pierre; Flacau, Roxana; Boyer, Chad; Feng, Zimin; Colombo, Massimo; Marras, Sergio; Prato, Mirko; Manna, Liberato; Guerfi, Abdelbast; Demopoulos, George P; Armand, Michel; Zaghib, Karim

    2016-04-13

    Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

  7. Enhancement of the Rate Capability of LiFePO4 by a New Highly Graphitic Carbon-Coating Method.

    PubMed

    Song, Jianjun; Sun, Bing; Liu, Hao; Ma, Zhipeng; Chen, Zhouhao; Shao, Guangjie; Wang, Guoxiu

    2016-06-22

    Low lithium ion diffusivity and poor electronic conductivity are two major drawbacks for the wide application of LiFePO4 in high-power lithium ion batteries. In this work, we report a facile and efficient carbon-coating method to prepare LiFePO4/graphitic carbon composites by in situ carbonization of perylene-3,4,9,10-tetracarboxylic dianhydride during calcination. Perylene-3,4,9,10-tetracarboxylic dianhydride containing naphthalene rings can be easily converted to highly graphitic carbon during thermal treatment. The ultrathin layer of highly graphitic carbon coating drastically increased the electronic conductivity of LiFePO4. The short pathway along the [010] direction of LiFePO4 nanoplates could decrease the Li(+) ion diffusion path. In favor of the high electronic conductivity and short lithium ion diffusion distance, the LiFePO4/graphitic carbon composites exhibit an excellent cycling stability at high current rates at room temperature and superior performance at low temperature (-20 °C). PMID:27238368

  8. Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

    PubMed

    Paolella, Andrea; Turner, Stuart; Bertoni, Giovanni; Hovington, Pierre; Flacau, Roxana; Boyer, Chad; Feng, Zimin; Colombo, Massimo; Marras, Sergio; Prato, Mirko; Manna, Liberato; Guerfi, Abdelbast; Demopoulos, George P; Armand, Michel; Zaghib, Karim

    2016-04-13

    Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances. PMID:26966938

  9. Synthesis, characterization and vibrational spectroscopic study of Co, Mg co-doped LiMnPO4

    NASA Astrophysics Data System (ADS)

    Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

    2016-01-01

    The isostructural olivine-like LiM(II)PO4 compounds [M(II) = Mn, Mn0.9Co0.1, Mn0.8Co0.1Mg0.1] were successfully generated through the solid state reaction from the synthesized NH4M(II)PO4• H2O precursors. The TG/DTG/DTA, AAS/AES, FTIR and XRD methods were employed to confirm both NH4M(II)PO4• H2O and LiM(II)PO4 compounds. Their morphologies were studied by SEM method. The shift of two theta angle of XRD to higher values was observed in metal doping compounds, which indicate the formation of the single phase of isodivalent doping of Co2 + and Mg2 + ions according to the change in the lattice parameters and cell volumes. Their infrared spectra are reported and discussed with respect to the normal vibrations of NH4+, PO43 -, P2O74 - and H2O molecules using factor group analysis. The correlation field splitting analysis of PO43 - in NH4M(II)PO4• H2O (orthorhombic system, Pmn21, C2v7 and Z = 2, [(3 × 5) - 6] × 2 = 18 internal modes) symbolized as Td - Cs - C2v7 suggested the number of vibrational modes to be: ΓVib = A1(6) + A2(3) + B1(6) + B2(3) and A1(6) + A2(3) + B1(3) + B2(6) for zx and yz plane respectively. While, LiM(II)PO4 crystallizes in the orthorhombic system the space group Pnma (D2h16), Z = 4 and the site symmetry of PO43 - is Cs. The correlation field splitting of type Td - Cs - D2h16 were reported in relation to [(3 × 5) - 6] × 4 = 36 internal modes for PO43 - unit in the structure.

  10. A chemically activated graphene-encapsulated LiFePO4 composite for high-performance lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Ha, Jeonghyun; Park, Seung-Keun; Yu, Seung-Ho; Jin, Aihua; Jang, Byungchul; Bong, Sungyool; Kim, In; Sung, Yung-Eun; Piao, Yuanzhe

    2013-08-01

    A composite of modified graphene and LiFePO4 has been developed to improve the speed of charging-discharging and the cycling stability of lithium ion batteries using LiFePO4 as a cathode material. Chemically activated graphene (CA-graphene) has been successfully synthesized via activation by KOH. The as-prepared CA-graphene was mixed with LiFePO4 to prepare the composite. Microscopic observation and nitrogen sorption analysis have revealed the surface morphologies of CA-graphene and the CA-graphene/LiFePO4 composite. Electrochemical properties have also been investigated after assembling coin cells with the CA-graphene/LiFePO4 composite as a cathode active material. Interestingly, the CA-graphene/LiFePO4 composite has exhibited better electrochemical properties than the conventional graphene/LiFePO4 composite as well as bare LiFePO4, including exceptional speed of charging-discharging and excellent cycle stability. That is because the CA-graphene in the composite provides abundant porous channels for the diffusion of lithium ions. Moreover, it acts as a conducting network for easy charge transfer and as a divider, preventing the aggregation of LiFePO4 particles. Owing to these properties of CA-graphene, LiFePO4 could demonstrate enhanced and stably long-lasting electrochemical performance.A composite of modified graphene and LiFePO4 has been developed to improve the speed of charging-discharging and the cycling stability of lithium ion batteries using LiFePO4 as a cathode material. Chemically activated graphene (CA-graphene) has been successfully synthesized via activation by KOH. The as-prepared CA-graphene was mixed with LiFePO4 to prepare the composite. Microscopic observation and nitrogen sorption analysis have revealed the surface morphologies of CA-graphene and the CA-graphene/LiFePO4 composite. Electrochemical properties have also been investigated after assembling coin cells with the CA-graphene/LiFePO4 composite as a cathode active material. Interestingly, the CA-graphene/LiFePO4 composite has exhibited better electrochemical properties than the conventional graphene/LiFePO4 composite as well as bare LiFePO4, including exceptional speed of charging-discharging and excellent cycle stability. That is because the CA-graphene in the composite provides abundant porous channels for the diffusion of lithium ions. Moreover, it acts as a conducting network for easy charge transfer and as a divider, preventing the aggregation of LiFePO4 particles. Owing to these properties of CA-graphene, LiFePO4 could demonstrate enhanced and stably long-lasting electrochemical performance. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr02738d

  11. Effects of imbalanced currents on large-format LiFePO4/graphite batteries systems connected in parallel

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Hu, Xiaosong; Jin, Chao; Jiang, Jiuchun; Zhang, Yanru; Yip, Tony

    2016-05-01

    With the development and popularization of electric vehicles, it is urgent and necessary to develop effective management and diagnosis technology for battery systems. In this work, we design a parallel battery model, according to equivalent circuits of parallel voltage and branch current, to study effects of imbalanced currents on parallel large-format LiFePO4/graphite battery systems. Taking a 60 Ah LiFePO4/graphite battery system manufactured by ATL (Amperex Technology Limited, China) as an example, causes of imbalanced currents in the parallel connection are analyzed using our model, and the associated effect mechanisms on long-term stability of each single battery are examined. Theoretical and experimental results show that continuously increasing imbalanced currents during cycling are mainly responsible for the capacity fade of LiFePO4/graphite parallel batteries. It is thus a good way to avoid fast performance fade of parallel battery systems by suppressing variations of branch currents.

  12. New freeze-drying method for LiFePO 4 synthesis

    NASA Astrophysics Data System (ADS)

    Palomares, Verónica; Goñi, Aintzane; Muro, Izaskun Gil de; de Meatza, Iratxe; Bengoechea, Miguel; Miguel, Oscar; Rojo, Teófilo

    The freeze-drying method is proposed as an effective synthesis process for the obtaining of LiFePO 4/C composites. The citric acid is used as a complexing agent and carbon source. After the low temperature annealing, the freeze-dried solution leads to a homogeneous carbon covered LiFePO 4 sample. The chemical characterization of the material included ICP and elemental analysis, infrared spectroscopy, X-ray diffraction, magnetic measurements and thermal analysis. SEM and TEM microscopies indicate an aggregate morphology with tiny particles of lithium iron phosphate inside a carbon matrix. Impedance spectroscopy showed a 8.0 × 10 -7 S cm -1 conductivity value. Cyclic voltammetry graphics displayed the two peaks corresponding to the Fe(II)/Fe(III) reaction and demonstrated the good reversibility of the material. The specific capacity value obtained at C/40 rate was 164 mAh g -1, with a slight decrease on greater C-rates reaching 146 mAh g -1 at C/1. The capacity retention study has evidenced good properties, with retention over 97% of the maximum values in the first 50 cycles, which allows an effective performance of the freeze-dried sample as cathodic material in lithium-ion batteries.

  13. Ab-initio Calculation of the XANES of Lithium Phosphates and LiFePO4

    NASA Astrophysics Data System (ADS)

    Yiu, Y. M.; Yang, Songlan; Wang, Dongniu; Sun, Xueliang; Sham, T. K.

    2013-04-01

    Lithium iron phosphate has been regarded as a promising cathode material for the next generation lithium ion batteries due to its high specific capacity, superior thermal and cyclic stability [1]. In this study, the XANES (X-ray Absorption Near Edge Structure) spectra of lithium iron phosphate and lithium phosphates of various compositions at the Li K, P L3,2, Fe M3,2 and O K-edges have been simulated self-consistently using ab-initio calculations based on multiple scattering theory (the FEFF9 code) and DFT (Density Functional Theory, the Wien2k code). The lithium phosphates under investigation include LiFePO4, γ-Li3PO4, Li4P2O7 and LiPO3. The calculated spectra are compared to the experimental XANES recorded in total electron yield (TEY) and fluorescence yield (FLY). This work was carried out to assess the XANES of possible phases presented in LiFePO4 based Li ion battery applications [2].

  14. Preparation and electrochemical properties of carbon-coated LiFePO4 hollow nanofibers

    NASA Astrophysics Data System (ADS)

    Wei, Bin-bin; Wu, Yan-bo; Yu, Fang-yuan; Zhou, Ya-nan

    2016-04-01

    Carbon-coated LiFePO4 hollow nanofibers as cathode materials for Li-ion batteries were obtained by coaxial electrospinning. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller specific surface area analysis, galvanostatic charge-discharge, and electrochemical impedance spectroscopy (EIS) were employed to investigate the crystalline structure, morphology, and electrochemical performance of the as-prepared hollow nanofibers. The results indicate that the carbon-coated LiFePO4 hollow nanofibers have good long-term cycling performance and good rate capability: at a current density of 0.2C (1.0C = 170 mA·g-1) in the voltage range of 2.5-4.2 V, the cathode materials achieve an initial discharge specific capacity of 153.16 mAh·g-1 with a first charge-discharge coulombic efficiency of more than 97%, as well as a high capacity retention of 99% after 10 cycles; moreover, the materials can retain a specific capacity of 135.68 mAh·g-1, even at 2C.

  15. Synthesis of carbon-coated LiFePO 4 nanoparticles with high rate performance in lithium secondary batteries

    NASA Astrophysics Data System (ADS)

    Konarova, Muxina; Taniguchi, Izumi

    A novel preparation technique was developed for synthesizing carbon-coated LiFePO 4 nanoparticles through a combination of spray pyrolysis (SP) with wet ball milling (WBM) followed by heat treatment. Using this technique, the preparation of carbon-coated LiFePO 4 nanoparticles was investigated for a wide range of process parameters such as ball-milling time and ball-to-powder ratio. The effect of process parameters on the physical and electrochemical properties of the LiFePO 4/C composite was then discussed through the results of X-ray diffraction (XRD) analysis, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), the Brunauer-Emmet-Teller (BET) method and the use of an electrochemical cell of Li|1 M LiClO 4 in EC:DEC = 1:1|LiFePO 4. The carbon-coated LiFePO 4 nanoparticles were prepared at 500 °C by SP and then milled at a rotating speed of 800 rpm, a ball-to-powder ratio of 40/0.5 and a ball-milling time of 3 h in an Ar atmosphere followed by heat treatment at 600 °C for 4 h in a N 2 + 3% H 2 atmosphere. SEM observation revealed that the particle size of LiFePO 4 was significantly affected by the process parameters. Furthermore, TEM observation revealed that the LiFePO 4 nanoparticles with a geometric mean diameter of 146 nm were coated with a thin carbon layer of several nanometers by the present method. Electrochemical measurement demonstrated that cells containing carbon-coated LiFePO 4 nanoparticles could deliver markedly improved battery performance in terms of discharge capacity, cycling stability and rate capability. The cells exhibited first discharge capacities of 165 mAh g -1 at 0.1 C, 130 mAh g -1 at 5 C, 105 mAh g -1 at 20 C and 75 mAh g -1 at 60 C with no capacity fading after 100 cycles.

  16. Effects of magnesium doping on electronic conductivity and electrochemical properties of LiFePO 4 prepared via hydrothermal route

    NASA Astrophysics Data System (ADS)

    Ou, Xiuqin; Liang, Guangchuan; Wang, Li; Xu, Shengzhao; Zhao, Xia

    Carbon free composites Li 1- xMg xFePO 4 (x = 0.00, 0.02) were synthesized from LiOH, H 3PO 4, FeSO 4 and MgSO 4 through hydrothermal route at 180 °C for 6h followed by being fired at 750 °C for 6 h. The samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), flame atomic absorption spectroscopy and electronic conductivity measurement. To investigate their electrochemical properties, the samples were mixed with glucose as carbon precursors, and fired at 750 °C for 6 h. The charge-discharge curves and cycle life test were carried out at 23 ± 2 °C. The Rietveid refinement results of lattice parameters of the samples indicate that the magnesium ion has been successfully doped into the M1 (Li) site of the phospho-olivine structure. With the same order of magnitude, there is no material difference in terms of the electronic conductivities between the doped and undoped composites. Conductivities of the doped and undoped samples are 10 -10 S cm -1 before being fired, 10 -9 S cm -1 after being fired at 750 °C, and 10 -1 S cm -1 after coated with carbon, respectively. Both the doped and undoped composites coated with carbon exhibit comparable specific capacities of 146 mAh g -1 vs. 144 mAh g -1 at 0.2 C, 140 mAh g -1 vs. 138 mAh g -1 at 1 C, and 124 mAh g -1 vs. 123 mAh g -1 at 5 C, respectively. The capacity retention rates of both doped and undoped samples over 50 cycles at 5 C are close to 100% (vs. the first-cycle corresponding C-rate capacity). Magnesium doping has little effects on electronic conductivity and electrochemical properties of LiFePO 4 composites prepared via hydrothermal route.

  17. Thermal annealing dynamics of carbon-coated LiFePO4 nanoparticles studied by in-situ analysis

    NASA Astrophysics Data System (ADS)

    Krumeich, Frank; Waser, Oliver; Pratsinis, Sotiris E.

    2016-10-01

    The thermal behavior of core-shell carbon-coated lithium iron phosphate (LiFePO4-C) nanoparticles made by flame spray pyrolysis (FSP) during annealing was investigated by in-situ transmission electron microscopy (TEM), in-situ X-ray powder diffraction (XRD) as well as ex-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Crystallization of the initially glassy LiFePO4-C nanoparticles starts at quite low temperatures (T=400 °C), forming single crystals inside the confinement of the carbon shell. Upon increasing the temperature to T≥700 °C, LiFePO4 starts to diffuse through the carbon shell resulting in cavities inside the mostly intact carbon shell. By increasing the temperature further to T≥800 °C, the initial core-shell morphology converts into open carbon shells (flakes and cenospheres) and bulky LiFePO4 particles (diameter in the range 300-400 nm), in agreement with ex-situ experiments.

  18. Effect of precursor concentration on the electrical properties of LiFePO4 prepared by solvothermal method

    NASA Astrophysics Data System (ADS)

    Rabbani, Ahmad Yasin; Fakhri, Hafizh A.; Arifin, Muhammad; Aimon, Akfiny Hasdi; Iskandar, Ferry

    2016-02-01

    Lithium iron phosphate (LiFePO4) is frequently used for Li-ion battery cathode. LiFePO4 has the high specific capacity at 170 mAhg-1, stable voltage at 3.45 V, stable structure, cheap, and low toxicity. The objective of this research is investigating the effect of precursor concentration on the electrical properties of LiFePO4 prepared by solvothermal method. LiOH, FeSO4, H3PO4, and citric acid were used as the precursors. The LiOH concentration was varied from 0.3 M to 1.8 M. The Fourier Transform Infrared Spectroscopy (FTIR) measurement identified the Fe-O, O-P-O, and P-O bonds which corresponding to LiFePO4. The result of 4-point probe measurement shows that, among the prepared samples, the sample from the precursor concentration of 1.8 M has the highest electrical conductivity.

  19. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

    NASA Astrophysics Data System (ADS)

    Jena, Ajit; Nanda, B. R. K.

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3-. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator.

  20. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

    PubMed Central

    Jena, Ajit; Nanda, B. R. K.

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3−. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

  1. Effect of surfactants on the electrochemical behavior of LiFePO4 cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Mandal, B. P.; Nazri, M.; Naik, V. M.; Garg, V. K.; Oliveira, A. C.; Vaishnava, P. P.; Nazri, G. A.; Naik, R.

    2014-11-01

    The application of lithium iron phosphate as positive electrode material for lithium ion batteries has been challenged by its poor electronic conductivity. To improve its conductivity and electrochemical performance, we have synthesized LiFePO4/C composite cathode materials by sol gel technique using long chain fatty acids, such as, lauric, myristic, and oleic acids, as surfactants for carbon coating. The phase purity of the three LiFePO4/C composites was confirmed by X-ray diffraction. The Raman spectroscopy, scanning electron microscopy and transmission electron microscopy measurements show that the surfactants coat the LiFePO4 particles with carbon with varying degree of uniformity depending on the surfactant used. The sample prepared in presence of lauric acid shows smaller particle size and the lowest charge transfer resistance, higher Li-ion diffusion coefficient, higher discharge capacity (∼155 mAh g-1 at C/3 rate), better rate capability and cyclic stability compared to the other two samples. We found the smaller particle size, uniformity of carbon coating, reduced agglomeration, and a lower amount of Fe3+ impurity phase in the samples to be major contributing factors for better electrochemical properties in the LiFePO4/C cathode material.

  2. Excess lithium storage in LiFePO4-Carbon interface by ball-milling

    NASA Astrophysics Data System (ADS)

    Guo, Hua; Song, Xiaohe; Zheng, Jiaxin; Pan, Feng

    2016-07-01

    As one of the most popular cathode materials for high power lithium ion batteries (LIBs) of the electrical-vehicle (EV), lithium iron phosphate (LiFePO4 (LFP)) is limited to its relatively lower theoretical specific capacity of 170mAh g‑1. To break the limits and further improve the capacity of LFP is promising but challenging. In this study, the ball-milling method is applied to the mixture of LFP and carbon, and the effective capacity larger than the theoretical one by 30mAh g‑1 is achieved. It is demonstrated that ball-milling leads to the LFP-Carbon interface to store the excess Li-ions.

  3. Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO4

    NASA Astrophysics Data System (ADS)

    Toft-Petersen, Rasmus; Reehuis, Manfred; Jensen, Thomas B. S.; Andersen, Niels H.; Li, Jiying; Le, Manh Duc; Laver, Mark; Niedermayer, Christof; Klemke, Bastian; Lefmann, Kim; Vaknin, David

    2015-07-01

    We report significant details of the magnetic structure and spin dynamics of LiFePO4 obtained by single-crystal neutron scattering. Our results confirm a previously reported collinear rotation of the spins away from the principal b axis, and they determine that the rotation is toward the a axis. In addition, we find a significant spin-canting component along c . The possible causes of these components are discussed, and their significance for the magnetoelectric effect is analyzed. Inelastic neutron scattering along the three principal directions reveals a highly anisotropic hard plane consistent with earlier susceptibility measurements. Using a spin Hamiltonian, we show that the spin dimensionality is intermediate between X Y - and Ising-like, with an easy b axis and a hard c axis. It is shown that both next-nearest neighbor exchange couplings in the b c plane are in competition with the strongest nearest neighbor coupling.

  4. Effects of TiO 2 coating on high-temperature cycle performance of LiFePO 4-based lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chang, Hao-Hsun; Chang, Chun-Chih; Su, Ching-Yi; Wu, Hung-Chun; Yang, Mo-Hua; Wu, Nae-Lih

    LiFePO 4 particles were coated with TiO 2 (molar ratio = 3%) via a sol-gel process, and the effects of the coating on cycle performance of LiFePO 4 cathode at 55 °C against either a Li or a C (mesocarbon microbead) anode were investigated. It was found that, while the coating reduces capacity fading of the LiFePO 4/Li cell, it imposes a deteriorating effect on the LiFePO 4/C cell. Analyses on cell impedance and electrode surface morphology and composition showed that the oxide coating reduced Fe dissolution from the LiFePO 4 cathode and hence alleviated the impedance increase associated with the erosion process. This leads to reduced capacity fading as observed for the LiFePO 4/Li cell. However, the oxide coating itself was eroded upon cycling, and the dissolved Ti ions were subsequently reduced at the anode surface. Ti deposit on the C anode was found to be more active than Fe in catalyzing the formation of the solid-electrolyte interphase (SEI) layer, causing accelerated capacity decay for the LiFePO 4/C cell. The results point out the importance of evaluating the effect of cathode coating material on the anode side, which has generally been overlooked in the past studies.

  5. Synthesis of LiFePO4/Li2SiO3/reduced Graphene Oxide (rGO) Composite via Hydrothermal Method

    NASA Astrophysics Data System (ADS)

    Arifin, M.; Iskandar, F.; Aimon, A. H.; Munir, M. M.; Nuryadin, B. W.

    2016-08-01

    LiFePO4 is a type of cathode active material used for lithium ion batteries. It has a high electrochemical performance. However, it suffers from certain disadvantages such as a very low intrinsic electronic conductivity and low ionic diffusion. This study was conducted to increase the conductivity of LiFePO4. We have investigated the addition of Li2SiO3 and reduced graphene oxide (rGO) to LiFePO4. The objective of this research was to synthesize LiFePO4/Li2SiO3/rGO via hydrothermal method. Fourier transform infrared spectroscopy (FTIR) measurement showed that the peaks corresponded to the vibration of LiFePO4/Li2SiO3. Further, X-ray diffraction (XRD) measurement confirmed a single phase of LiFePO4. Finally, scanning electron microscopy (SEM) images showed that rGO was distributed on the LiFePO4/Li2SiO3 structure.

  6. Encapsulation of LiFePO4 by in-situ graphitized carbon cage towards enhanced low temperature performance as cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yao, Bin; Ding, Zhaojun; Zhang, Jianxin; Feng, Xiaoyu; Yin, Longwei

    2014-08-01

    The severe capacity decay of LiFePO4 at low temperatures (≤0 °C) limits its wide applications as cathode materials for energy storage batteries. Creating comprehensive carbon network between particles with improved electronic conductivity is a well known solution to this problem. Here, a novel structured LiFePO4/C composite was prepared by a facile solid state route, in which nanosized LiFePO4 spheres were encapsulated by in-situ graphitized carbon cages. With the enhancement in electronic conductivity (2.15e-1 S cm-1), the composite presented excellent rate performance at room temperature and remarkable capacity retention at -40 °C, with charge transfer resistance much lower than commercial LiFePO4.

  7. Formation mechanism of LiFePO 4/C composite powders investigated by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Hsu, Kuei-Feng; Hu, Shao-Kang; Chen, Chinh-Hsiang; Cheng, Ming-Yao; Tsay, Sun-Yuan; Chou, Tse-Chuan; Sheu, Hwo-Shuenn; Lee, Jyh-Fu; Hwang, Bing-Joe

    The local structure and oxidation states for both the precursors and the LiFePO 4/C composite powders were investigated by X-ray absorption spectroscopy (XAS) to provide a deep insight into their formation mechanism. It was found that the local structure and oxidation states of the precursors and the synthesized LiFePO 4/C powders as well as the electrochemical properties of the synthesized powders were strongly influenced by the R ratio (R: molar ratio of citric acid to total metal ions). The oxidation states of iron ions of the precursors for R = 1 and 0.75 consist mainly of Fe(II) and traces of Fe(III). However, the oxidation state of iron ions of the precursor for R = 0.5 comprises mainly of Fe(III). The oxidation state of iron ions of all the synthesized powders is Fe(II). The structure of the precursors and the synthesized powders for R = 1 and 0.75 is more ordering than that for R = 0.5. It is in good agreement with the observation of the cation mixing obtained from the Riteveld analysis of the XRD data. The better the electrochemical performance is, the more ordering the structure or the less the cation mixing. However, the effect of the R values on the carbon content is also essential for the electrochemical properties of the synthesized LiFePO 4/C composite powders. Increasing the carbon content leads to the increase in the electronic conductivity but impedes the Li + ion diffusion of the composite materials. Consequently, the powders synthesized at the optimal R ratio of 0.75 exhibited the highest initial capacity, about 150 mAh g -1 when cycled at 1/40 C rate at room temperature. The structural scheme of the precursors and the synthesized powders and the formation mechanism of the LiFePO 4/C composite powders are also addressed in this work.

  8. Nanoscale LiFePO4 and Li4Ti5O12 for High Rate Li-ion Batteries

    SciTech Connect

    Jaiswal, A.; Horne, C.R.; Chang, O.; Zhang, W.; Kong, W.; Wang, E.; Chern, T.; Doeff, M. M.

    2009-08-04

    The electrochemical performances of nanoscale LiFePO4 and Li4Ti5O12 materials are described in this communication. The nanomaterials were synthesized by pyrolysis of an aerosol precursor. Both compositions required moderate heat-treatment to become electrochemically active. LiFePO4 nanoparticles were coated with a uniform, 2-4 nm thick carbon-coating using an organic precursor in the heat treatment step and showed high tap density of 1.24 g/cm3, in spite of 50-100 nm particle size and 2.9 wtpercent carbon content. Li4Ti5O12 nanoparticles were between 50-200 nm in size and showed tap density of 0.8 g/cm3. The nanomaterials were tested both in half cell configurations against Li-metal and also in LiFePO4/Li4Ti5O12 full cells. Nano-LiFePO4 showed high discharge rate capability with values of 150 and 138 mAh/g at C/25 and 5C, respectively, after constant C/25 charges. Nano-Li4Ti5O12 also showed high charge capability with values of 148 and 138 mAh/g at C/25 and 5C, respectively, after constant C/25 discharges; the discharge (lithiation) capability was comparatively slower. LiFePO4/Li4Ti5O12 full cells deliver charge/discharge capacity values of 150 and 122 mAh/g at C/5 and 5C, respectively.

  9. Phase boundary propagation in large LiFePO4 single crystals on delithiation.

    PubMed

    Weichert, Katja; Sigle, Wilfried; van Aken, Peter A; Jamnik, Janez; Zhu, Changbao; Amin, Ruhul; Acartürk, Tolga; Starke, Ulrich; Maier, Joachim

    2012-02-15

    Large single crystals of LiFePO(4) have been chemically delithiated. The relevance of chemical oxidation in comparison with electrochemical delithiation is discussed. Analyses of the Li content and profiles were done by electron energy loss spectroscopy and secondary ion mass spectrometry. The propagation of the FePO(4) phase growing on the surface of the large single crystal was followed by in situ optical microscopy as a function of time. The kinetics were evaluated in terms of linear irreversible thermodynamics and found to be characterized by an induction period followed by parabolic growth behavior of the FePO(4) phase indicating transport control. The growth rate was shown to depend on the crystallographic orientation. Scanning electron microscopy images showed cracks and a high porosity of the FePO(4) layer due to the significant changes in the molar volumes. The transport was found to be greatly enhanced by the porosity and crack formation and hence greatly enhanced over pure bulk transport, a result which is supposed to be very relevant for battery research if coarse-grained powder is used.

  10. Degradation diagnosis of aged Li4Ti5O12/LiFePO4 batteries

    NASA Astrophysics Data System (ADS)

    Castaing, Rémi; Reynier, Yvan; Dupré, Nicolas; Schleich, Donald; Jouanneau Si Larbi, Séverine; Guyomard, Dominique; Moreau, Philippe

    2014-12-01

    Li4Ti5O12/LiFePO4 cells are cycled under 4 different conditions of discharge profile (galvanostatic or driving-based) and cycling rates (C/8 or 1C) during 4-5 months. All the cells exhibit capacity fade whose extent is not correlated with the aging condition. In order to understand aging phenomena, cells are disassembled at the end of cycle life and the recovered electrodes are analyzed using electrochemistry, electron microscopy, XRD and MAS-NMR. Positive and negative electrodes show no loss in active material and no change in electrochemical activity, active material structure and composite electrode structure. This rules out any irreversible electrode degradation. Lithium stoichiometry estimated by both XRD and electrochemistry is unexpectedly low in the positive electrode when the aging is stopped at full discharge. That indicates a loss of cyclable lithium or electrons leading to cell balancing evolution. That loss may have been caused by parasitic reactions occurring at both electrodes, in accordance with their rich surface chemistry as evidenced by MAS-NMR.

  11. Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO4

    DOE PAGESBeta

    Toft-Petersen, Rasmus; Reehuis, Manfred; Jensen, Thomas B. S.; Andersen, Niels H.; Li, Jiying; Le, Manh Duc; Laver, Mark; Niedermayer, Christof; Klemke, Bastian; Lefmann, Kim; et al

    2015-07-06

    We report significant details of the magnetic structure and spin dynamics of LiFePO4 obtained by single-crystal neutron scattering. Our results confirm a previously reported collinear rotation of the spins away from the principal b axis, and they determine that the rotation is toward the a axis. In addition, we find a significant spin-canting component along c. Furthermore, the possible causes of these components are discussed, and their significance for the magnetoelectric effect is analyzed. Inelastic neutron scattering along the three principal directions reveals a highly anisotropic hard plane consistent with earlier susceptibility measurements. While using a spin Hamiltonian, we showmore » that the spin dimensionality is intermediate between XY- and Ising-like, with an easy b axis and a hard c axis. As a result, it is shown that both next-nearest neighbor exchange couplings in the bc plane are in competition with the strongest nearest neighbor coupling.« less

  12. Carbon-coated LiFePO4-porous carbon composites as cathode materials for lithium ion batteries.

    PubMed

    Ni, Haifang; Liu, Jinkun; Fan, Li-Zhen

    2013-03-01

    This work introduces a facile strategy for the synthesis of carbon-coated LiFePO(4)-porous carbon (C-LiFePO(4)-PC) composites as a cathode material for lithium ion batteries. The LiFePO(4) particles obtained are about 200 nm in size and homogeneously dispersed in porous carbon matrix. These particles are further coated with the carbon layers pyrolyzed from sucrose. The C-LiFePO(4)-PC composites display a high initial discharge capacity of 152.3 mA h g(-1) at 0.1 C, good cycling stability, as well as excellent rate capability (112 mA h g(-1) at 5 C). The likely contributing factors to the excellent electrochemical performance of the C-LiFePO(4)-PC composites could be related to the combined effects of enhancement of conductivity by the porous carbon matrix and the carbon coating layers. It is believed that further carbon coating is a facile and effective way to improve the electrochemical performance of LiFePO(4)-PC.

  13. Role of PO4 tetrahedron in LiFePO4 and FePO4 system.

    PubMed

    Zeng, Yuewu

    2015-06-01

    Using high resolution transmission electron microscopy with image simulation and Fourier analysis, the Li1- x FePO4 (x < 0.01), Li1- x FePO4 (x ∼ 0.5), and FePO4 particles, prepared by charging or discharging the 053048 electrochemical cells (thickness: 5 mm, width: 30 mm, height: 48 mm) and dismantled inside an Ar-filled dry box, were investigated. The high resolution images reveal: (1) the solid solution of Li1- x FePO4 (x < 0.01) contains some missing Li ions leading PO4 group distorted around M1 tunnel of the unit cell; (2) the texture of the particles of Li1- x FePO4 (x ∼0.5) has homogeneously distributed compositional domains of LiFePO4 and FePO4 resulting from spinodal decomposition which promote Li ion easily getting into the particle due to uphill diffusion, (3) the particles of FePO4 formed in charging have heavily distorted lattice and contain some isolated LiFePO4 , (4) interface between LiFePO4 and FePO4 and between amorphous and crystal region provides the lattice distortion of small polarons.

  14. High-performance LiFePO4/C electrode with polytetrafluoroethylene as an aqueous-based binder

    NASA Astrophysics Data System (ADS)

    Gao, Shiyan; Su, Yuefeng; Bao, Liying; Li, Ning; Chen, Lai; Zheng, Yu; Tian, Jun; Li, Jian; Chen, Shi; Wu, Feng

    2015-12-01

    An environmental-friendly and low-cost polymer, polytetrafluoroethylene (PTFE) has been applied as an aqueous-based binder for the fabrication of LiFePO4/C electrode. The electrode with PTFE has been compared to the electrode with the conventional binder, polyvinylidene fluoride (PVDF) via Rheology test, X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and electrochemical tests. The Rheology test indicates that the viscosity of the slurry prepared with PTFE as a binder is better than that prepared with PVDF. The electrochemical measurements demonstrate that the electrode with PTFE binder displays a higher discharge capacity of 161.1 mAh g-1 compared to the electrode with PVDF binder, which shows a discharge capacity of 150.7 mAh g-1. The EIS analysis indicates the LiFePO4/C electrode with PTFE binder shows a higher ionic conductivity and a smaller increasing in charge transfer rate compared to the LiFePO4/C electrode with PVDF binder. In addition, the electrodes applying the aqueous-based binder have been optimized by controlling the moisture content in the electrodes. The electrochemical enhancement of these electrodes can be achieved by controlling the vacuum drying temperature and time during the preparation of the electrodes.

  15. Relating the 3D electrode morphology to Li-ion battery performance; a case for LiFePO4

    NASA Astrophysics Data System (ADS)

    Liu, Zhao; Verhallen, Tomas W.; Singh, Deepak P.; Wang, Hongqian; Wagemaker, Marnix; Barnett, Scott

    2016-08-01

    One of the main goals in lithium ion battery electrode design is to increase the power density. This requires insight in the relation between the complex heterogeneous microstructure existing of active material, conductive additive and electrolyte providing the required electronic and Li-ion transport. FIB-SEM is used to determine the three phase 3D morphology, and Li-ion concentration profiles obtained with Neutron Depth Profiling (NDP) are compared for two cases, conventional LiFePO4 electrodes and better performing carbonate templated LiFePO4 electrodes. This provides detailed understanding of the impact of key parameters such as the tortuosity for electron and Li-ion transport though the electrodes. The created hierarchical pore network of the templated electrodes, containing micron sized pores, appears to be effective only at high rate charge where electrolyte depletion is hindering fast discharge. Surprisingly the carbonate templating method results in a better electronic conductive CB network, enhancing the activity of LiFePO4 near the electrolyte-electrode interface as directly observed with NDP, which in a large part is responsible for the improved rate performance both during charge and discharge. The results demonstrate that standard electrodes have a far from optimal charge transport network and that significantly improved electrode performance should be possible by engineering the microstructure.

  16. Investigation on the fly ash thermal treatment on the performance of Lithium Ferriphosphate (LiFePO4) battery

    NASA Astrophysics Data System (ADS)

    Febiolita, Bella; Khoirunnissak, Dewi; Purwanto, Agus

    2016-02-01

    Addition of the fly ash can be used to improve the capacity of LiFePO4 battery. Fly ash was added in Acethylene Black (AB) as 2% of the total weight of Acetylene Black (AB). The effects of temperature variation and fly ash characteristics were analyzed. Fly ash was prepared by heating at 50, 100, 150, and 250°C in muffle furnace for 5 hours and passed in 200 mesh screen prior to mixing it with other compounds. Lithium Ferriphospat (LiFePO4), fly ash, Acethylene Black (AB), Polyvinylidene Fluoride (PVDF) as a binder and N-methyl-2-pyrrolidone (NMP) as a solvent were mixed to be slurry. The slurry were coated, dried and hot pressed to make a cathode film. The performance of battery lithium was examined by eight channel battery analyzer. The composition of the fly ash was examined by X-ray fluorescence spectrometry (XRF) and Fourier Tansform Infrared Spectroscopy (FTIR). The excellent performance was shown in the fly ash addition which were treated by heating at 150°C. The capacity of fly ash added LiFePO4 battery is 94.373 mAh/g, which is higher than that of without fly ash addition, i.e. 67.998 mAh/g.

  17. Surfactant based sol-gel approach to nanostructured LiFePO 4 for high rate Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Choi, Daiwon; Kumta, Prashant N.

    Porous nanostructured LiFePO 4 powder with a narrow particle size distribution (100-300 nm) for high rate lithium-ion battery cathode application was obtained using an ethanol based sol-gel route employing lauric acid as a surfactant. The synthesized LiFePO 4 powders comprised of agglomerates of crystallites <65 nm in diameter exhibiting a specific surface area ranging from 8 m 2 g -1 to 36 m 2 g -1 depending on the absence or presence of the surfactant. The LiFePO 4 obtained using lauric acid resulted in a specific capacity of 123 mAh g -1 and 157 mAh g -1 at discharge rates of 10 C and 1 C with less than 0.08% fade per cycle, respectively. Structural and microstructural characterization were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray (EDX) analysis while electronic conductivity and specific surface area were determined using four-point probe and N 2 adsorption techniques.

  18. In-situ synthesis of monodisperse micro-nanospherical LiFePO4/carbon cathode composites for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Gong, Hao; Xue, Hairong; Wang, Tao; He, Jianping

    2016-06-01

    The LiFePO4 is recognized as the promising cathode material, due to its high specific capacity, excellent, structural stability and environmental benignity. However, it is blamed for the low tap density and poor rate performance when served as the cathode materials for a long time. Here, the microspheric LiFePO4/C composites are successfully synthesized through a one-step in-situ solvothermal method combined with carbothermic reduction. These LiFePO4/C microspheres are assembled by LiFePO4 nanoparticles (∼100 nm) and uniformly coated by the carbon, which show a narrow diameter distribution of 4 μm. As a cathode material for lithium ion batteries, the LiFePO4/C composites can deliver an initiate charge capacity of 155 mAh g-1 and retain 90% of initial capacity after 200 cycles at 0.1 C. When cycled at high current densities up to 20 C, it shows a discharge capacity of ∼60 mAh g-1, exhibiting superior rate performance. The significantly improved electrochemical performance of LiFePO4/C composites material can be attributed to its special micro-nano hierarchical structure. Microspheric LiFePO4/C composites exhibit a high tap density about 1.3 g cm-3. What's more, the well-coated carbon insures the high electrical conductivity and the nano-sized LiFePO4/C particles shorten lithium ion transport, thus exhibiting the high specific capacity, high cycling stability and good rate performance.

  19. Boron and Nitrogen Codoped Carbon Layers of LiFePO4 Improve the High-Rate Electrochemical Performance for Lithium Ion Batteries.

    PubMed

    Zhang, Jinli; Nie, Ning; Liu, Yuanyuan; Wang, Jiao; Yu, Feng; Gu, Junjie; Li, Wei

    2015-09-16

    An evolutionary composite of LiFePO4 with nitrogen and boron codoped carbon layers was prepared by processing hydrothermal-synthesized LiFePO4. This novel codoping method is successfully applied to LiFePO4 for commercial use, and it achieved excellent electrochemical performance. The electrochemical performance can be improved through single nitrogen doping (LiFePO4/C-N) or boron doping (LiFePO4/C-B). When modifying the LiFePO4/C-B with nitrogen (to synthesis LiFePO4/C-B+N) the undesired nonconducting N-B configurations (190.1 and 397.9 eV) are generated. This decreases the electronic conductivity from 2.56×10(-2) to 1.30×10(-2) S cm(-1) resulting in weak electrochemical performance. Nevertheless, using the opposite order to decorate LiFePO4/C-N with boron (to obtain LiFePO4/C-N+B) not only eliminates the nonconducting N-B impurity, but also promotes the conductive C-N (398.3, 400.3, and 401.1 eV) and C-B (189.5 eV) configurations-this markedly improves the electronic conductivity to 1.36×10(-1) S cm(-1). Meanwhile the positive doping strategy leads to synergistic electrochemical activity distinctly compared with single N- or B-doped materials (even much better than their sum capacity at 20 C). Moreover, due to the electron and hole-type carriers donated by nitrogen and boron atoms, the N+B codoped carbon coating tremendously enhances the electrochemical property: at the rate of 20 C, the codoped sample can elevate the discharge capacity of LFP/C from 101.1 mAh g(-1) to 121.6 mAh g(-1), and the codoped product based on commercial LiFePO4/C shows a discharge capacity of 78.4 mAh g(-1) rather than 48.1 mAh g(-1). Nevertheless, the B+N codoped sample decreases the discharge capacity of LFP/C from 101.1 mAh g(-1) to 95.4 mAh g(-1), while the commercial LFP/C changes from 48.1 mAh g(-1) to 40.6 mAh g(-1).

  20. LiFePO4 nanoparticles enveloped in freestanding sandwich-like graphitized carbon sheets as enhanced remarkable lithium-ion battery cathode.

    PubMed

    Zhang, Yan; Zhang, Huijuan; Li, Xiao; Xu, Haitao; Wang, Yu

    2016-04-15

    A novel nanostructure where LiFePO4 nanoparticles are enveloped in sandwich-like carbon sheets as an enhanced cathode in lithium-ion batteries has successfully been synthesized for the first time. Compared to previous carbon-based nanocomposites, the achieved sandwich-like LiFePO4 nanocomposites exhibit totally different architecture, in which LiFePO4 nanoparticles are tightly entrapped between two carbon layers, instead of being anchored on the carbon sheet surfaces. In other words, the achieved sandwich-like LiFePO4 nanocomposite carbon layers are actually freestanding and can be operated and separated from each other. This is a great breakthrough in the design and synthesis of carbon-based functional materials. The obtained sandwich-like LiFePO4 nanocomposites present excellent electrochemical performance, which is rationally ascribed to the superb and unique structure and architecture. Of particular note is that the freestanding sandwich-like LiFePO4 nanocomposites exhibit enhanced cyclability and rate capability. At a high current density of 0.1 A g(-1), a stable specific capacity of approximately 168.5 mAh g(-1) can be delivered over 1000 cycles, and when the charge-discharge rates increase to 0.6, 2, 5 and 10 A g(-1), the specific capacities still survive at 149, 129, 114 and 91 mAh g(-1), respectively. Meanwhile, the sandwiched nanocomposite demonstrates a significantly improved low-temperature electrochemical energy storage performance. With respect to the excellent Li storage performance, and facility and reliability of production, the freestanding sandwich-like LiFePO4 nanocomposites are reasonably believed to have a great potential for multiple electrochemical energy storage applications.

  1. Excellent temperature performance of spherical LiFePO4/C composites modified with composite carbon and metal oxides.

    PubMed

    Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

    2014-01-01

    Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO4 ·2H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO4 ·2H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7 mAh·g(-1) at a 0.1 C rate, 152.4 mAh·g(-1) at a 1 C rate and 131.7 mAh·g(-1) at a 5 C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55°C, 0°C, -10°C, and -20°C by comparison withthat of room temperature (25°C) at the 0.5 C rate over a voltage range of 2.2 V to 3.6 V, respectively.

  2. In situ high-resolution transmission electron microscopy synthesis observation of nanostructured carbon coated LiFePO 4

    NASA Astrophysics Data System (ADS)

    Trudeau, M. L.; Laul, D.; Veillette, R.; Serventi, A. M.; Mauger, A.; Julien, C. M.; Zaghib, K.

    In situ high-resolution transmission electron microscopy (HRTEM) studies of the structural transformations that occur during the synthesis of carbon-coated LiFePO 4 (C-LiFePO 4) and heat treatment to elevated temperatures were conducted in two different electron microscopes. Both microscopes have sample holders that are capable of heating up to 1500 °C, with one working under high vacuum and the other capable of operating with the sample surrounded by a low gaseous environment. The C-LiFePO 4 samples were prepared using three different compositions of precursor materials with Fe(0), Fe(II) or Fe(III), a Li-containing salt and a polyethylene- block-poly(ethylene glycol)-50% ethylene oxide or lactose. The in situ TEM studies suggest that low-cost Fe(0) and a low-cost carbon-containing compound such as lactose are very attractive precursors for mass production of C-LiFePO 4, and that 700 °C is the optimum synthesis temperature. At temperatures higher than 800 °C, LiFePO 4 has a tendency to decompose. The same in situ measurements have been made on particles without carbon coat. The results show that the homogeneous deposit of the carbon deposit at 700 °C is the result of the annealing that cures the disorder of the surface layer of bare LiFePO 4. Electrochemical tests supported the conclusion that the C-LiFePO 4 derived from Fe(0) is the most attractive for mass production.

  3. Excellent Temperature Performance of Spherical LiFePO4/C Composites Modified with Composite Carbon and Metal Oxides

    PubMed Central

    Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

    2014-01-01

    Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO4·2H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO4·2H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7 mAh·g−1 at a 0.1 C rate, 152.4 mAh·g−1 at a 1 C rate and 131.7 mAh·g−1 at a 5 C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55°C, 0°C, −10°C, and −20°C by comparison withthat of room temperature (25°C) at the 0.5 C rate over a voltage range of 2.2 V to 3.6 V, respectively. PMID:24526888

  4. Lithium potential variations for metastable materials: case study of nanocrystalline and amorphous LiFePO4.

    PubMed

    Zhu, Changbao; Mu, Xiaoke; Popovic, Jelena; Weichert, Katja; van Aken, Peter A; Yu, Yan; Maier, Joachim

    2014-09-10

    Much attention has been paid to metastable materials in the lithium battery field, especially to nanocrystalline and amorphous materials. Nonetheless, fundamental issues such as lithium potential variations have not been pertinently addressed. Using LiFePO4 as a model system, we inspect such lithium potential variations for various lithium storage modes and evaluate them thermodynamically. The conclusions of this work are essential for an adequate understanding of the behavior of electrode materials and even helpful in the search for new energy materials.

  5. Reversible chemical delithiation/lithiation of LiFePO4: towards a redox flow lithium-ion battery.

    PubMed

    Huang, Qizhao; Li, Hong; Grätzel, Michael; Wang, Qing

    2013-02-14

    Reversible chemical delithiation/lithiation of LiFePO(4) was successfully demonstrated using ferrocene derivatives, based on which a novel energy storage system--the redox flow lithium-ion battery (RFLB), was devised by integrating the operation flexibility of a redox flow battery and high energy density of a lithium-ion battery. Distinct from the recent semi-solid lithium rechargeable flow battery, the energy storage materials of RFLB stored in separate energy tanks remain stationary upon operation, giving us a fresh perspective on building large-scale energy storage systems with higher energy density and improved safety.

  6. Influence of memory effect on the state-of-charge estimation of large-format Li-ion batteries based on LiFePO4 cathode

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Wang, Jiulin; Zheng, Jianming; Jiang, Jiuchun; Viswanathan, Vilayanur; Zhang, Ji-Guang

    2016-04-01

    In this work, we systematically investigated the influence of the memory effect of LiFePO4 cathodes in large-format full batteries. The electrochemical performance of the electrodes used in these batteries was also investigated separately in half-cells to reveal their intrinsic properties. We noticed that the memory effect of LiFePO4/graphite cells depends not only on the maximum state of charge reached during the memory writing process, but is also affected by the depth of discharge reached during the memory writing process. In addition, the voltage deviation in a LiFePO4/graphite full battery is more complex than in a LiFePO4/Li half-cell, especially for a large-format battery, which exhibits a significant current variation in the region near its terminals. Therefore, the memory effect should be taken into account in advanced battery management systems to further extend the long-term cycling stabilities of Li-ion batteries using LiFePO4 cathodes.

  7. Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability

    PubMed Central

    Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

    2016-01-01

    A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li+ diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe3+ to Fe2+ and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li+ intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method. PMID:27181195

  8. Long-term cycle stability at a high current for nanocrystalline LiFePO4 coated with a conductive polymer

    NASA Astrophysics Data System (ADS)

    Dinh, Hung-Cuong; Lim, Hanjo; Park, Ki Dong; Yeo, In-Hyeong; Kang, Yongku; Mho, Sun-il

    2013-03-01

    Highly uniform hierarchical-microstructured LiFePO4 particles with dumbbell- and donut-shape and individual LiFePO4 nanocrystals were prepared by a hydrothermal method utilizing citric acid or a triblock copolymer (Pluronic P123) as a surfactant. The cathode composed of the individual nanocrystalline LiFePO4 particles exhibited higher specific capacity than the cathodes composed of the hierarchically assembled microparticles. Coating a conductive polymer, poly-3,4-ethylenedioxythiophene (PEDOT), on the surface of LiFePO4 particles improved the battery performances such as large specific capacities, high rate capability and an improved cycle stability. The nanocrystalline LiFePO4 particles coated with PEDOT (20 wt%) exhibited the highest discharge capacities of 175 and 136 mAh g-1 for the first battery cycle and 163 and 128 mAh g-1 after 500 battery cycles, with a degradation rate of 6-7%, at the rates of 1 and 10 C, respectively.

  9. Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability

    NASA Astrophysics Data System (ADS)

    Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

    2016-05-01

    A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li+ diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe3+ to Fe2+ and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li+ intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method.

  10. Li-Ion Battery with LiFePO4 Cathode and Li4Ti5O12 Anode for Stationary Energy Storage

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Choi, Daiwon; Yang, Zhenguo

    2013-01-01

    Li-ion batteries based on commercially available LiFePO4 cathode and Li4Ti5O12 anode were investigated for potential stationary energy storage applications. The full cell that operated at flat 1.85 V demonstrated stable cycling up to 200 cycles followed by a rapid fade. A Li-ion full cell with Ketjen black modified LiFePO4 cathode and an unmodified Li4Ti5O12 anode exhibited negligible fade after more than 1200 cycles with a capacity of ~130 mAh/g at C/2. The improved stability, along with its cost-effectiveness, environmental benignity, and safety, make the LiFePO4/Li4Ti5O12 combination Li-ion battery a promising option for storing renewable energy.

  11. Li-Ion Battery with LiFePO4 Cathode and Li4Ti5O12 Anode for Stationary Energy Storage

    SciTech Connect

    Wang, Wei; Choi, Daiwon; Yang, Zhenguo

    2013-01-01

    i-ion batteries based on commercially available LiFePO4 cathode and Li4Ti5O12 anode were investigated for potential stationary energy storage applications. The full cell that operated at flat 1.85V demonstrated stable cycling for 200 cycles followed by a rapid fade. A significant improvement in cycling stability was achieved via Ketjen black coating of the cathode. A Li-ion full cell with Ketjen black modified LiFePO4 cathode and an unmodified Li4Ti5O12 anode exhibited negligible fade after more than 1200 cycles with a capacity of ~130mAh/g. The improved stability, along with its cost-effectiveness, environmentally benignity and safety, make the LiFePO4/ Li4Ti5O12 Li-ion battery a promising option of storing renewable energy.

  12. Impact of carbon structure and morphology on the electrochemical performance of LiFePO4/C composites

    SciTech Connect

    Doeff, Marca M.; Doeff, Marca M.; Wilcox, James D.; Yu, Rong; Aumentado, Albert; Marcinek, Marek; Kostecki, Robert

    2007-09-19

    The electrochemical performance of LiFePO4/C composites in lithium cells is closely correlated to pressed pellet conductivities measured by AC impedance methods. These composite conductivities are a strong function not only of the amount of carbon but of its structure and distribution. Ideally, the amount of carbon in composites should be minimal (less than about 2 wtpercent) so as not to decrease the energy density unduly. This is particularly important for plug-in hybrid electric vehicle applications (PHEVs) where both high power and moderate energy density are required. Optimization of the carbon structure, particularly the sp2/sp3 and disordered/graphene (D/G) ratios, improves the electronic conductivity while minimizing the carbon amount. Manipulation of the carbon structure can be achieved via the use of synthetic additives including ironcontaining graphitization catalysts. Additionally, combustion synthesis techniques allow co-synthesis of LiFePO4 and carbon fibers or nanotubes, which can act as"nanowires" for the conduction of current during cell operation.

  13. Double Carbon Nano Coating of LiFePO4 Cathode Material for High Performance of Lithium Ion Batteries.

    PubMed

    Ding, Yan-Hong; Huang, Guo-Long; Li, Huan-Huan; Xie, Hai-Ming; Sun, Hai-Zhu; Zhang, Jing-Ping

    2015-12-01

    Double carbon-coated LiFePO4 (D-LiFePO4/C) composite with sphere-like structure was synthesized through combination of co-precipitation and solid-state methods. Cetyl-trimethyl-ammonium bromide (CTAB) and citric acid served as two kinds of carbon sources in sequence. SEM images demonstrated that double carbon coating had certain influence on the morphology. The thickness of carbon coating on D-LiFePO4/C was about 1.7 nm and the content of carbon was 2.48 wt%, according to HRTEM and TG analysis. The electrochemical impedance spectroscopy analysis indicated that the D-LiFePO4/C composite presented the charge-transfer resistance of 68 Ω and Li ion diffusion coefficient of 2.68 x 10(-13) cm2 S(-1), while the single carbon-coated LiFePO4 (S-LiFePO4/C) exhibited 135.5Ω and 4.03 x 10(-14) cm2 S(-1). Especially, the prepared D-LiFePO4/C electrode showed discharge capacities of 102.9 (10C) and 87.1 (20C) mA h g(-1), respectively, with almost no capacity lost after 400 cycles at 10C, which were much better than those of S-LiFePO4/C composite.

  14. Physical and electrochemical properties of LiFePO 4 nanoparticles synthesized by a combination of spray pyrolysis with wet ball-milling

    NASA Astrophysics Data System (ADS)

    Konarova, Muxina; Taniguchi, Izumi

    A novel preparation technique was developed to synthesize LiFePO 4 nanoparticles through a combination of spray pyrolysis (SP) with wet ball-milling (WBM). Using this technique, the preparation of LiFePO 4 nanoparticles was investigated for a wide range of process parameters such as ball-milling time and sintering temperature. The effect of process parameters on the physical and electrochemical properties of LiFePO 4 was then discussed through analysis using by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), the Brunauer-Emmet-Teller (BET) method, Raman spectroscopy and using an electrochemical cell of Li|1 M LiClO 4 in EC:DEC = 1:1|LiFePO 4. LiFePO 4 nanoparticles with a geometric mean diameter of 58 nm were prepared at a rotating speed of 800 rpm and a ball-milling time of 12 h in an Ar atmosphere followed by heat treatment at 500 °C for 4 h in a N 2 + 3% H 2 atmosphere. The sample delivered first discharge capacities of 164 and 100 mAh g -1 at charge-discharge rates of 0.1 and 10 C in the test cells, respectively. The electrochemical properties of LiFePO 4 nanoparticles were strongly affected by the formation of Fe 2P, Fe 3P and α-Fe 2O 3 at higher charge-discharge rates.

  15. Interphase evolution at two promising electrode materials for Li-ion batteries: LiFePO4 and LiNi1/2 Mn1/2O2.

    PubMed

    Dupré, Nicolas; Cuisinier, Marine; Martin, Jean-Frederic; Guyomard, Dominique

    2014-07-21

    The present review reports the characterization and control of interfacial processes occurring on olivine LiFePO(4) and layered LiNi(1/2) Mn(1/2)O(2), standing here as model compounds, during storage and electrochemical cycling. The formation and evolution of the interphase created by decomposition of the electrolyte is investigated by using spectroscopic tools such as magic-angle-spinning nuclear magnetic resonance ((7)Li,(19)F and (31)P) and electron energy loss spectroscopy, in parallel to X-ray photoelectron spectroscopy, to quantitatively describe the interphase and unravel its architecture. The influence of the pristine surface chemistry of the active material is carefully examined. The importance of the chemical history of the surface of the electrode material before any electrochemical cycling and the strong correlation between interface phenomena, the formation/evolution of an interphase, and the electrochemical behavior appear clearly from the use of these combined characterization probes. This approach allows identifying interface aging and failure mechanisms. Different types of surface modifications are then investigated, such as intrinsic modifications upon aging in air or methods based on the use of additives in the electrolyte or carbon coatings on the surface of the active materials. In each case, the species detected on the surface of the materials during storage and cycling are correlated with the electrochemical performance of the modified positive electrodes.

  16. Etched Colloidal LiFePO4 Nanoplatelets toward High-Rate Capable Li-Ion Battery Electrodes

    PubMed Central

    2014-01-01

    LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently “plagued” by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼155 mAh/g, ∼135 mAh/g, and ∼125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries. PMID:25372361

  17. Synthesis of LiFePO 4/C composite with high-rate performance by starch sol assisted rheological phase method

    NASA Astrophysics Data System (ADS)

    Huang, Yanghui; Ren, Haibo; Yin, Shengyu; Wang, Yunhong; Peng, Zhenghe; Zhou, Yunhong

    LiFePO 4/C composite was synthesized at 600 °C in an Ar atmosphere by a soluble starch sol assisted rheological phase method using home-made amorphous nano-FePO 4 as the iron source. XRD, SEM and TEM observations show that the LiFePO 4/C composite has good crystallinity, ultrafine sphere-like particles of 100-200 nm size and in situ carbon. The synthesized LiFePO 4 could inherit the morphology of FePO 4 precursor. The electrochemical performance of the LiFePO 4 by galvanostatic cycling studies demonstrates excellent high-rate cycle stability. The Li/LiFePO 4 cell displays a high initial discharge capacity of more than 157 mAh g -1 at 0.2C and a little discharge capacity decreases from the first to the 80th cycle (>98.3%). Remarkably, even at a high current density of 30C, the cell still presents good cycle retention.

  18. Effect of Surfactants on the Physical Properties and Electrochemical Performance of LiFePO4 Cathode Material for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Naik, R.; Nazri, G. A.; Nazri, M.; Naik, V.; Mandal, B. P.; Vaishnava, P. P.

    2012-10-01

    Use of lithium iron phosphate in lithium ion battery is hampered by the poor electronic conductivity and slow lithium ion diffusion. Several methods have been tried to improve the conductivity. Carbon coating is found to be very suitable way to enhance the electronic conductivity. Here, we report synthesis of carbon coated LiFePO4 composite materials using lauric, myristic, and oleic acid as source of carbon. The phase purity of these three LiFePO4/C composites was confirmed by X-Ray Diffraction. The quality of carbon coating has been investigated by Raman spectroscopy. In all the samples, the carbon content is found to be approximately 10%. SEM and TEM investigations reveal that the surfactants coat the LiFePO4 particles uniformly with carbon and the coating reduces the particle size to approximately 30 nm. Due to high electrical conductivity, controlled particle size and suitable microstructure, among the three LiFePO4 coated samples, the sample prepared in presence of lauric acid exhibited superior electrochemical performance in terms of specific capacity, the cycling stability and delivered high discharge capacity of ˜140 mAhg-1 at C/2 rate.

  19. Atomic-Scale Observations of (010) LiFePO4 Surfaces Before and After Chemical Delithiation.

    PubMed

    Kobayashi, Shunsuke; Fisher, Craig A J; Kato, Takeharu; Ukyo, Yoshio; Hirayama, Tsukasa; Ikuhara, Yuichi

    2016-09-14

    The ability to view directly the surface structures of battery materials with atomic resolution promises to dramatically improve our understanding of lithium (de)intercalation and related processes. Here we report the use of state-of-the-art scanning transmission electron microscopy techniques to probe the (010) surface of commercially important material LiFePO4 and compare the results with theoretical models. The surface structure is noticeably different depending on whether Li ions are present in the topmost surface layer or not. Li ions are also found to migrate back to surface regions from within the crystal relatively quickly after partial delithiation, demonstrating the facile nature of Li transport in the [010] direction. The results are consistent with phase transformation models involving metastable phase formation and relaxation, providing atomic-level insights into these fundamental processes. PMID:27472440

  20. Ink-jet printed porous composite LiFePO4 electrode from aqueous suspension for microbatteries

    NASA Astrophysics Data System (ADS)

    Delannoy, P.-E.; Riou, B.; Brousse, T.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

    2015-08-01

    This work demonstrates ink-jet printed LiFePO4-based composite porous electrodes for microbattery application. As binder and dispersant, we found that aqueous inks with more suitable rheological properties with respect to ink-jet printing are prepared with the low molecular weight poly-acrylic-co-maleic acid copolymer, rather than with the carboxymethyl cellulose standard binder of the lithium-ion technology. The ink-jet printed thin and porous electrode shows very high rate charge/discharge behavior, both in LiPF6/ethylene carbonate-dimethyl carbonate (LP30) and lithium bis(trifluoromethane)sulfonylimide salt (Li-TFSI) in N-methyl-N-propylpyrrolidinium bis(trifluoromethane)suflonylimide ionic liquid (PYR13-TFSI) electrolytes, as well as good cyclability.

  1. LiFePO4 Nanostructures Fabricated from Iron(III) Phosphate (FePO4 x 2H2O) by Hydrothermal Method.

    PubMed

    Saji, Viswanathan S; Song, Hyun-Kon

    2015-01-01

    Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures.

  2. Enhancement of electrochemical performances for LiFePO4/C with 3D-grape-bunch structure and selection of suitable equivalent circuit for fitting EIS results

    NASA Astrophysics Data System (ADS)

    Li, Xiangfeng; Luo, Dongmei; Zhang, Xin; Zhang, Zhao

    2015-09-01

    The LiFePO4/C composite with 3D-grape-bunch structure is successfully synthesized through a novel hydrothermal method. Sucrose is used as in-situ coating carbon source, and the hydroxylated MWCNTs are used as connecting carbon wires which can be embedded into the carbon coating via self-assembling of the hydrophilic groups to form 3D-grape-bunch structure. The influences of the 3D-grape-bunch structure on the morphology, structure and electrochemical performance of the LiFePO4/C composites are investigated by XRD, SEM, TEM, BET, galvanostatic charge/discharge tests, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) tests. Especially, four kinds of the equivalent circuit models usually employed to analysis the EISs of LiFePO4 as cathode material for Li-ion battery are discussed, and the suitable equivalent circuit for fitting EIS of LiFePO4/C composite with 3D-grape-bunch structure is selected. The optimal LiFePO4/C composite with 3D-grape-bunch structure owing to its good conductive network and high graphitic degree (low ID/IG value) of residual carbon exhibits a stable and high reversible capacity of 160.5 mAh g-1 at 0.1C and 108.4 mAh g-1 even at 10.0C, and the cycling capacity retention rate reaches 99.9% over 60 cycles. Moreover, it also exhibits high conductivity, good reversibility and excellent stability in EIS and CV tests.

  3. LiFePO4 Nanostructures Fabricated from Iron(III) Phosphate (FePO4 x 2H2O) by Hydrothermal Method.

    PubMed

    Saji, Viswanathan S; Song, Hyun-Kon

    2015-01-01

    Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures. PMID:26328435

  4. Olivines and olivine coronas in mesosiderites

    NASA Technical Reports Server (NTRS)

    Nehru, C. E.; Zucker, S. M.; Harlow, G. E.; Prinz, M.

    1980-01-01

    The paper presents a study of olivines and their surrounding coronas in mesosiderites texturally and compositionally using optical and microprobe methods. Olivine composition ranges from Fo(58-92) and shows no consistent pattern of distribution within and between mesosiderites; olivine occurs as large single crystals or as partially recrystallized mineral clasts, except for two lithic clasts. These are Emery and Vaca Muerta, and both are shock-modified olivine orthopyroxenites. Fine-grained coronas surround olivine, except for those in impact-melt group mesosiderites and those without tridymite in their matrices. Coronas consist largely of orthopyroxene, plagioclase, clinopyroxene, chromite, merillite, and ilmenite, and are similar to the matrix, but lack metal and tridymite. Texturally the innermost parts of the corona can be divided into three stages of development: (1) radiating acicular, (2) intermediate, and (3) granular.

  5. A method for state-of-charge estimation of LiFePO4 batteries based on a dual-circuit state observer

    NASA Astrophysics Data System (ADS)

    Tang, Xiaopeng; Wang, Yujie; Chen, Zonghai

    2015-11-01

    Estimation of state-of-charge (SOC) is a key criterion to evaluate the battery management system (BMS). Due to the flat open-circuit voltage (OCV)-SOC curve of LiFePO4 batteries, it is a great challenge to estimate the SOC accurately. Here we present a dual-circuit state observer for SOC estimation of LiFePO4 batteries. It is a combination of an open loop based current integrator and a proportional-integral (PI) based state observer. We also employed an easy but practical drifting current corrector to restrain the influence of the drifting current. The experiment results show that error of the estimated SOC is less than 2.5% by the proposed method when the initial SOC is unknown. We proved that with no matrix operations, the proposed method is lighted-weighted and high efficient, which is suitable for embedded systems.

  6. Electrical and electrochemical characterization of nano-sized LiFePO4 cathode materials synthesized by a lauric acid-based sol--gel method

    NASA Astrophysics Data System (ADS)

    Bazzi, Khadije; Dixit, Ambesh; Naik, Ratna; Naik, Vaman; Vaishnava, Prem; Nazri, Abbas; Nazri, Mariam

    2011-04-01

    We synthesized pure LiFePO4 and C-LiFePO4 nanoparticles by sol-gel technique. Carbon coating was accomplished by including Lauric acid in the sol-gel precursor solution. Three C-LiFePO4 samples of particle sizes 29, 27, 23 nm, were prepared by varying lauric acid concentration in the precursor solution. All the samples were characterized by X-ray diffraction, Raman, conductivity, and electrochemical measurements. The micro-Raman measurements showed two major bands at 1350 and 1590 cm-1 respectively (ID/IG) and the electronic conductivity were found to depend strongly on the amount of surfactant coverage. The 23 nm particle size sample showed minimum (D/G) band ratio and the maximum electrical conductivity among the three samples. The measured value of the capacity for 23 nm sized sample, ˜ 170 mAh/g, approached the theoretical capacity limit value for LiFePO4

  7. Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism.

    PubMed

    Seifitokaldani, Ali; Gheribi, Aïmen E; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

    2016-01-01

    A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures. PMID:27604551

  8. Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism.

    PubMed

    Seifitokaldani, Ali; Gheribi, Aïmen E; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

    2016-09-08

    A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures.

  9. Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

    NASA Astrophysics Data System (ADS)

    Seifitokaldani, Ali; Gheribi, Aïmen E.; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

    2016-09-01

    A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures.

  10. Fast charging technique for high power LiFePO4 batteries: A mechanistic analysis of aging

    NASA Astrophysics Data System (ADS)

    Anseán, D.; Dubarry, M.; Devie, A.; Liaw, B. Y.; García, V. M.; Viera, J. C.; González, M.

    2016-07-01

    One of the major issues hampering the acceptance of electric vehicles (EVs) is the anxiety associated with long charging time. Hence, the ability to fast charging lithium-ion battery (LIB) systems is gaining notable interest. However, fast charging is not tolerated by all LIB chemistries because it affects battery functionality and accelerates its aging processes. Here, we investigate the long-term effects of multistage fast charging on a commercial high power LiFePO4-based cell and compare it to another cell tested under standard charging. Coupling incremental capacity (IC) and IC peak area analysis together with mechanistic model simulations ('Alawa' toolbox with harvested half-cell data), we quantify the degradation modes that cause aging of the tested cells. The results show that the proposed fast charging technique caused similar aging effects as standard charging. The degradation is caused by a linear loss of lithium inventory, coupled with a less degree of linear loss of active material on the negative electrode. This study validates fast charging as a feasible mean of operation for this particular LIB chemistry and cell architecture. It also illustrates the benefits of a mechanistic approach to understand cell degradation on commercial cells.

  11. Heat loss distribution: Impedance and thermal loss analyses in LiFePO4/graphite 18650 electrochemical cell

    NASA Astrophysics Data System (ADS)

    Balasundaram, Manikandan; Ramar, Vishwanathan; Yap, Christopher; Lu, Li; Tay, Andrew A. O.; Palani, Balaya

    2016-10-01

    We report here thermal behaviour and various components of heat loss of 18650-type LiFePO4/graphite cell at different testing conditions. In this regard, the total heat generated during charging and discharging processes at various current rates (C) has been quantified in an Accelerating Rate Calorimeter experiment. Irreversible heat generation, which depends on applied current and internal cell resistance, is measured under corresponding charge/discharge conditions using intermittent pulse techniques. On the other hand, reversible heat generation which depends on entropy changes of the electrode materials during the cell reaction is measured from the determination of entropic coefficient at various states of charge/discharge. The contributions of irreversible and reversible heat generation to the total heat generation at both high and low current rates are evaluated. At every state of charge/discharge, the nature of the cell reaction is found to be either exothermic or endothermic which is especially evident at low C rates. In addition, electrochemical impedance spectroscopy measurements are performed on above 18650 cells at various states of charge to determine the components of internal resistance. The findings from the impedance and thermal loss analysis are helpful for understanding the favourable states of charge/discharge for battery operation, and designing better thermal management systems.

  12. Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

    PubMed Central

    Seifitokaldani, Ali; Gheribi, Aïmen E.; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

    2016-01-01

    A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures. PMID:27604551

  13. Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling

    PubMed Central

    Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P.; Brownrigg, Alex; Wright, Jonathan P.; van Dijk, Niels H.; Wagemaker, Marnix

    2015-01-01

    Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements. PMID:26395323

  14. Combined operando X-ray diffraction–electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

    PubMed Central

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-01-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

  15. Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

    NASA Astrophysics Data System (ADS)

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-09-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ~20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4.

  16. Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries.

    PubMed

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-09-08

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4.

  17. In-situ growth of graphene decorations for high-performance LiFePO4 cathode through solid-state reaction

    NASA Astrophysics Data System (ADS)

    Li, Jing; Zhang, Li; Zhang, Longfei; Hao, Weiwei; Wang, Haibo; Qu, Qunting; Zheng, Honghe

    2014-03-01

    Graphene-decorated LiFePO4 composite is synthesized for the first time through in-situ pyrolysis and catalytic graphitization, in which glucose and a trace amount of FeSO4 are employed as the graphene source and catalyst precursor, respectively. Under Ar/H2 (95:5) atmosphere at 750 °C, FeSO4 is thermally reduced to Fe nano-particles (Fe NPs) and glucose is pyrolyzed to carbon fragments first, followed by the in-situ growth of graphene sheets directly on the LiFePO4 nano-particles (LFP NPs) surface through the realignment of carbon fragments under the catalytic effect of the Fe NPs. The graphene sheets not only form a compact and uniform coating layer throughout the LFP NPs, but also stretch out and cross-link into a conducting network around the LFP particles. The LiFePO4@graphene composite displays a high reversible specific capacity of 167.7 mAh g-1 at 0.1C rate, superb rate performance with discharge capacity of 94.3 mAh g-1 at 100C rate and much prolonged cycle life. The remarkable electrochemical improvement is attributed to both electric and ionic conductivity increase as a result of in-situ grown graphene coatings along the LFP surface and the graphene network intrinsically connecting to the LFP particles.

  18. Core-shell LiFePO4 /carbon-coated reduced graphene oxide hybrids for high-power lithium-ion battery cathodes.

    PubMed

    Ha, Sung Hoon; Lee, Yun Jung

    2015-01-26

    Core-shell carbon-coated LiFePO4 nanoparticles were hybridized with reduced graphene (rGO) for high-power lithium-ion battery cathodes. Spontaneous aggregation of hydrophobic graphene in aqueous solutions during the formation of composite materials was precluded by employing hydrophilic graphene oxide (GO) as starting templates. The fabrication of true nanoscale carbon-coated LiFePO4 -rGO (LFP/C-rGO) hybrids were ascribed to three factors: 1) In-situ polymerization of polypyrrole for constrained nanoparticle synthesis of LiFePO4 , 2) enhanced dispersion of conducting 2D networks endowed by colloidal stability of GO, and 3) intimate contact between active materials and rGO. The importance of conducting template dispersion was demonstrated by contrasting LFP/C-rGO hybrids with LFP/C-rGO composites in which agglomerated rGO solution was used as the starting templates. The fabricated hybrid cathodes showed superior rate capability and cyclability with rates from 0.1 to 60 C. This study demonstrated the synergistic combination of nanosizing with efficient conducting templates to afford facile Li(+) ion and electron transport for high power applications.

  19. Electronic structure of phospho-olivines LixFePO4 (x=0,1) fromsoft-x-ray-absorption and -emission spectroscopies

    SciTech Connect

    Augustsson, A.; Zhuang, G.V.; Butorin, S.M.; Osorio-Guillen,J.M.; Dong, C.L.; Ahuja, R.; Chang, C.L.; Ross, P.N.; Nordgren, J.; Guo,J.-H.

    2005-07-17

    The electronic structure of the phospho-olivine LixFePO4 wasstudied using soft-x-ray-absorption (XAS) and emission spectroscopies.Characteristic changes in the valence and conduction bands are observedupon delithation of LiFePO4 into FePO4. In LiFePO4, the Fe-3d states arelocalized with little overlap with the O-2p states. Delithiation ofLiFePO4 gives stronger hybridization between Fe-3d states and O-2p statesleading to delocalization of the O-2p states. The Fe L-edge absorptionspectra yield "fingerprints" of the different valence states of Fe inLiFePO4 and FePO4. Resonant soft-x-ray-emission spectroscopy at the Fe Ledge shows strong contributions from resonant inelastic soft x-rayscattering (RIXS), which is described using an ionic picture of the Fe-3dstates. Together the Fe L-edge XAS and RIXS study reveals a bondingcharacter of the Fe 3d-O2p orbitals in FePO4 in contrast to a nonbondingcharacter in LiFePO4.

  20. Tungsten diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.; Van Orman, J. A.

    2014-03-01

    Diffusion of tungsten has been characterized in synthetic forsterite and natural olivine (Fo90) under dry conditions. The source of diffusant was a mixture of magnesium tungstate and olivine powders. Experiments were prepared by sealing the source material and polished olivine under vacuum in silica glass ampoules with solid buffers to buffer at NNO or IW. Prepared capsules were annealed in 1 atm furnaces for times ranging from 45 min to several weeks, at temperatures from 1050 to 1450 °C. Tungsten distributions in the olivine were profiled by Rutherford Backscattering Spectrometry (RBS). The following Arrhenius relation is obtained for W diffusion in forsterite: D=1.0×10-8exp(-365±28 kJ mol/RT) m s Diffusivities for the synthetic forsterite and natural Fe-bearing olivine are similar, and tungsten diffusion in olivine shows little dependence on crystallographic orientation or oxygen fugacity. The slow diffusivities measured for W in olivine indicate that Hf-W ages in olivine-metal systems will close to diffusive exchange at higher temperatures than other chronometers commonly used in cosmochronology, and that tungsten isotopic signatures will be less likely to be reset by subsequent thermal events.

  1. Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries

    PubMed Central

    2014-01-01

    The phase changes that occur during discharge of an electrode comprised of LiFePO4, carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate. PMID:24790684

  2. A method for state-of-charge estimation of LiFePO4 batteries at dynamic currents and temperatures using particle filter

    NASA Astrophysics Data System (ADS)

    Wang, Yujie; Zhang, Chenbin; Chen, Zonghai

    2015-04-01

    The state-of-charge (SOC) estimation for LiFePO4 batteries is one of the most important issues in battery management system (BMS) on electric vehicles (EVs). Significant temperature changes and drift current noises are inevitable in EVs and cause strong interference in SOC estimation, therefore a SOC-Particle filter (PF) estimator is proposed for SOC estimation. This paper tries to make three contributions: (1) a temperature composed battery model is established based on commercial LiFePO4 cells which can be used for SOC estimation at dynamic temperatures. (2) A capacity retention ratio (CRR) aging model is established based on the real history statistical analysis of the running mileage of the battery on an urban bus. (3) The proposed models are combined with an electrochemical model and the PF method is employed for SOC estimation to eliminate the drift noise effects. Experiments under dynamic current and temperature conditions are designed and performed to verify the accuracy and robustness of the proposed method. The numeral results of the validation experiments have verified that accurate and robust SOC estimation results can be obtained by the proposed method.

  3. Effect of Surfactants on the Physical Properties and Electrochemical Performance of LiFePO4 Cathode Material for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Nazri, M.; Vaishnava, P.; Naik, V. M.; Nazri, G. A.; Naik, R.

    2012-02-01

    The lithium iron phosphate chemistry is plagued by the poor electronic conductivity and slow lithium ion diffusion in the solid phase. In order to solve these problems, various research groups have adopted different strategies including decreasing the particle size, covering the particles with carbon, and adding dopants to the cathode material. Here, we report synthesis of C-LiFePO4 cathode materials using 0.25M lauric, myristic, and oleic acid as surfactants. The phase purity of all three C-LiFePO4 was confirmed by x-ray diffraction. SEM and TEM investigations reveal that the surfactants coat the LiFePO4 particles uniformly with carbon and the coating reduces the particle size to 20-30 nm. Due to high electrical conductivity, controlled particle size and suitable microstructure, among the three LiFePO4 coated samples, the sample with 0.25M lauric acid exhibited superior electrochemical performance in terms of specific capacity, the cycling stability and delivered high discharge capacity of 155, 150 and 123 mAhg-1 at 0.5 C, 1C and 5C, respectively. The correlation between the ratio of the intensities of the D and G bands observed by micro-Raman spectroscopy, conductivity and electrochemical characteristics will be presented.

  4. Electrochemical performance of La2O3/Li2O/TiO2 nano-particle coated cathode material LiFePO4.

    PubMed

    Wang, Hong; Yang, Chi; Liu, Shu-Xin

    2014-09-01

    Cathode material, LiFePO4 was modified by coating with a thin layer of La2O3/Li2O/TiO2 nano-particles for improving its performance for lithium ion batteries. The morphology and structure of the modified cathode material were characterized by powder X-ray diffraction, scanning electron microcopy and AES. The performance of the battery with the modified cathode material, including cycling stability, C-rate discharge was examined. The results show that the battery composed of the coated cathode materials can discharge at a large current density and show stable cycling performance in the range from 2.5 to 4.0 V. The rate of Li ion diffusion increases in the battery with the La2O3/Li2O/TiO2-coated LiFePO4 as a cathode and the coating layer may acts as a faster ion conductor (La(2/3-x)Li(3x)TiO3).

  5. A novel dual-salts of LiTFSI and LiODFB in LiFePO4-based batteries for suppressing aluminum corrosion and improving cycling stability

    NASA Astrophysics Data System (ADS)

    Li, Faqiang; Gong, Yan; Jia, Guofeng; Wang, Qinglei; Peng, Zhengjun; Fan, Wei; Bai, Bing

    2015-11-01

    The strong corrosion behavior at the Al current collector restricts the application range of lithium bis (trifluoromethanesulfonylimide) (LiTFSI), despite its high stability against water and thermal. SEM, LSV and Tafel curves proved that adding LiODFB into LiTFSI-based electrolytes could suppress aluminum corrosion caused by LiTFSI-based electrolytes. The cycling stability and rate capability of LiFePO4-based batteries using LiTFSI0.6-LiODFB0.4-based electrolytes is excellent as compared to LiFePO4-based batteries using LiPF6-based electrolytes.

  6. Performance qualification and Raman investigation on cell behavior and aging of LiFePO4 cathodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Salehi, Amir

    This thesis explores the ability of Raman spectroscopy to understand the complex chemistry taking place in LiFePO4 cathodes of Li ion batteries. The performance of Li ion batteries was optimized through electrode fabrication and assembling procedures. Various amounts of Timcal Super P carbon were used to construct a conductive network of C-LiFePO4 particles and the performance of the cathodes was examined during battery cycling. Raman spectroscopy along with electrochemical characterization such as charge/ discharge curves, electrochemical impedance spectroscopy and Cyclic Voltammetry was employed for detailed investigation of battery performance and aging. It is found that both quantity and quality of the conductive carbon affect the rate performance and cyclic behavior of the cells. The cathodes with 2% additive carbon showed a faster capacity fading during cycling than that with 10% additive carbon due to a quicker degradation of the conductive network as indicated by sp2/sp3 and ID/IG ratios in Raman spectroscopy results. The rate performance of cathodes with 2%, 10% and 20 % carbon was also compared and a better rate performance was found for 2% carbon. It showed a proper electronic network which is mostly provided by carbon coating along with a large pore size of the cathode which facilitates the electrolyte penetration. Furthermore, in situ Raman spectroscopy was employed to probe electrolyte concentration variation at the cathode LiFePO4 particle surface in an optically transparent lithium ion cell. A Raman laser spot size of 2 microm was applied so that transport dynamics at individual particle surface could be investigated. The variation of Li+ concentration in the LiPF6/ethylene carbonate (EC) + dimethyl carbonate (DMC) electrolyte was determined, for the first time. This was done by monitoring the C--O stretching vibration signal intensity and the corresponding relationship to EC solvation. The electrolyte concentration at the LiFePO 4 particle surface was found to fluctuate during the battery charge/discharge cycle. Particularly, near the end of battery discharge, it reached to a minimum value which was far less than its initial balanced value (1 mol.dm -3).

  7. Pilot-scale continuous synthesis of a vanadium-doped LiFePO4/C nanocomposite high-rate cathodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Johnson, Ian D.; Lübke, Mechthild; Wu, On Ying; Makwana, Neel M.; Smales, Glen J.; Islam, Husn U.; Dedigama, Rashmi Y.; Gruar, Robert I.; Tighe, Christopher J.; Scanlon, David O.; Corà, Furio; Brett, Dan J. L.; Shearing, Paul R.; Darr, Jawwad A.

    2016-01-01

    A high performance vanadium-doped LiFePO4 (LFP) electrode is synthesized using a continuous hydrothermal method at a production rate of 6 kg per day. The supercritical water reagent rapidly generates core/shell nanoparticles with a thin, continuous carbon coating on the surface of LFP, which aids electron transport dynamics across the particle surface. Vanadium dopant concentration has a profound effect on the performance of LFP, where the composition LiFe0.95V0.05PO4, achieves a specific discharge capacity which is among the highest in the comparable literature (119 mA h g-1 at a discharge rate of 1500 mA g-1). Additionally, a combination of X-ray absorption spectroscopy analysis and hybrid-exchange density functional theory, suggest that vanadium ions replace both phosphorous and iron in the structure, thereby facilitating Li+ diffusion due to Li+ vacancy generation and changes in the crystal structure.

  8. Mixed salts of LiTFSI and LiBOB for stable LiFePO4-based batteries at elevated temperatures

    SciTech Connect

    Chen, Xilin; Xu, Wu; Engelhard, Mark H.; Zheng, Jianming; Zhang, Yaohui; Ding, Fei; Qian, Jiangfeng; Zhang, Ji-Guang

    2014-01-01

    To achieve stable long-term cycling stability at elevated temperatures, mixed salts of LiTFSI and LiBOB are used to replace LiPF6 salt in non-aqueous electrolytes for LiFePO4-based batteries. It is found that adding LiBOB in LiTFSI-based electrolytes effectively prevents the severe corrosion to Al current collectors that often is observed in LiTFSI-based electrolytes, which have high thermal stability. The cells using LiTFSI-LiBOB-based electrolytes demonstrate superior high temperature (60 °C) stability and very similar room temperature performance (i.e., cycling stability and rate capability) when compared to cells using the LiPF6-based electrolyte.

  9. Nanosized LiFePO4-decorated emulsion-templated carbon foam for 3D micro batteries: a study of structure and electrochemical performance

    NASA Astrophysics Data System (ADS)

    Asfaw, Habtom D.; Roberts, Matthew R.; Tai, Cheuk-Wai; Younesi, Reza; Valvo, Mario; Nyholm, Leif; Edström, Kristina

    2014-07-01

    In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium.In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01682c

  10. Rapid Microwave-Assisted Solvothermal Synthesis of Non-Olivine Cmcm Polymorphs of LiMPO4 (M = Mn, Fe, Co, and Ni) at Low Temperature and Pressure.

    PubMed

    Assat, Gaurav; Manthiram, Arumugam

    2015-10-19

    Lithium transition-metal phosphates, LiMPO4 (M = Mn, Fe, Co, and Ni), have attracted significant research interest over the past two decades as an important class of lithium ion battery cathode materials. However, almost all of the investigations thus far have focused on the olivine polymorph that exists in the orthorhombic Pnma space group. In this study, a distinct orthorhombic but non-olivine polymorph of LiMPO4, described by a Cmcm space group symmetry, has been synthesized with M = Mn, Fe, Co, and Ni. Of these, LiMnPO4 in the Cmcm space group is reported for the first time. A rapid microwave-assisted solvothermal (MW-ST) heating process with tetraethylene glycol (TEG) as the solvent and transition-metal oxalates as precursors facilitates the synthesis of these materials. The peak reaction temperatures and pressures were below 300 °C and 30 bar, respectively, which are several orders of magnitude lower than those of the previously reported high-pressure (gigapascals) method. X-ray diffraction (XRD) confirms the crystal structure with the Cmcm space group, and scanning electron micrographs indicate a submicrometer thin platelet-like morphology. The synthesis process conditions have been optimized to obtain impurity-free samples with the correct stoichiometry, as characterized by XRD and inductively coupled plasma-optical emission spectroscopy (ICP-OES). Upon heat treatment to higher temperatures, an irreversible transformation of the metastable Cmcm polymorphs into olivine is observed by XRD and Fourier transform infrared spectroscopy. Although the electrochemical activity of these polymorphs as lithium ion cathodes turns out to be poor, the facile synthesis under mild conditions has permitted easy access to these materials in a nanomorphology, some of which were not even possible before. PMID:26428928

  11. Microbial Weathering of Olivine

    NASA Technical Reports Server (NTRS)

    McKay, D. S.; Longazo, T. G.; Wentworth, S. J.; Southam, G.

    2002-01-01

    Controlled microbial weathering of olivine experiments displays a unique style of nanoetching caused by biofilm attachment to mineral surfaces. We are investigating whether the morphology of biotic nanoetching can be used as a biosignature. Additional information is contained in the original extended abstract.

  12. Surface-orientation-dependent distribution of subsurface cation-exchange defects in olivine-phosphate nanocrystals.

    PubMed

    Chung, Sung-Yoon; Choi, Si-Young; Kim, Tae-Hwan; Lee, Seongsu

    2015-01-27

    Atomic-scale exchange between two different cations of similar size in crystalline oxides is one of the major types of point defects when multiple cations in oxygen interstitials are arrayed in an ordered manner. Although a number of studies have been performed on a variety of Li-intercalation olivine phosphates to determine the distribution of exchange defects in bulk, understanding of the thermodynamic stability of the defects in subsurface regions and its dependency on the crystallographic orientation at the surface has remained elusive. Through a combination of small-angle neutron scattering, atomic-scale direct probing with scanning transmission electron microscopy, and theoretical ab initio calculations, we directly demonstrate that the antisite exchange defects are distributed in a highly anisotropic manner near the surfaces of LiFePO4 crystals. Moreover, a substantial amount of cation exchanges between Li and Fe sites is identified as an energetically favorable configuration in some surface regions, showing excellent agreement with the calculation results of negative defect formation energies. The findings in this study provide insight into developing better ways to avoid degradation of lithium mobility through the surface as well as scientifically notable features regarding the distribution of exchange defects in olivine phosphates.

  13. Helium Diffusion in Olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.; Watson, E. B.

    2011-12-01

    Diffusion of helium has been characterized in natural Fe-bearing olivine (~Fo90) and synthetic forsterite. Polished, oriented slabs of olivine were implanted with 3He, at 100 keV at a dose of 5x1015/cm2 or at 3.0 MeV at a dose of 1x1016/cm2. A set of experiments on the implanted olivine were run in 1-atm furnaces. In addition to the one-atm experiments, experiments on implanted samples were also run at higher pressures (2.6 and 2.7 GPa) to assess the potential effects of pressure on He diffusion and the applicability of the measured diffusivities in describing He transport in the mantle. The high-pressure experiments were conducted in a piston-cylinder apparatus using an "ultra-soft" pressure cell, with the diffusion sample directly surrounded by AgCl. 3He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. This direct profiling method permits us to evaluate anisotropy of diffusion, which cannot be easily assessed using bulk-release methods. For diffusion in forsterite parallel to c we obtain the following Arrhenius relation over the temperatures 250-950°C: D = 3.91x10-6exp(-159 ± 4 kJ mol-1/RT) m2/sec. The data define a single Arrhenius line spanning more than 7 orders of magnitude in D and 700°C in temperature. Diffusion parallel to a appears slightly slower, yielding an activation energy for diffusion of 135 kJ/mol and a pre-exponential factor of 3.73x10-8 m2/sec. Diffusion parallel to b is slower than diffusion parallel to a (by about two-thirds of a log unit); for this orientation an activation energy of 138 kJ/mol and a pre-exponential factor of 1.34x10-8 m2/sec are obtained. This anisotropy is broadly consistent with observations for diffusion of Ni and Fe-Mg in olivine. Diffusion in Fe-bearing olivine (transport parallel to b) agrees within uncertainty with findings for He diffusion in forsterite. The higher-pressure experiments yield diffusivities in agreement with those from the 1-atm

  14. High-resolution chemical analysis on cycled LiFePO4 battery electrodes using energy-filtered transmission electron microscopy

    NASA Astrophysics Data System (ADS)

    Sugar, Joshua D.; El Gabaly, Farid; Chueh, William C.; Fenton, Kyle R.; Tyliszczak, Tolek; Kotula, Paul G.; Bartelt, Norman C.

    2014-01-01

    We demonstrate an ex situ method for analyzing the chemistry of battery electrode particles after electrochemical cycling using the transmission electron microscope (TEM). The arrangement of particles during our analysis is the same as when the particles are being cycled. We start by sectioning LiFePO4 battery electrodes using an ultramicrotome. We then show that mapping of the Fe2+ and Fe3+ oxidation state using energy-filtered TEM (EFTEM) and multivariate statistical analysis techniques can be used to determine the spatial distribution of Li in the particles. This approach is validated by comparison with scanning transmission X-ray microscopy (STXM) analysis of the same samples [Chueh et al. Nanoletters, 13 (3) (2013) 866-72]. EFTEM uses a parallel electron beam and reduces the electron-beam dose (and potential beam-induced damage) to the sample when compared to alternate techniques that use a focused probe (e.g. STEM-EELS). Our analysis confirms that under the charging conditions of the analyzed battery, mixed phase particles are rare and thus Li intercalation is limited by the nucleation of new phases.

  15. Solvothermal synthesis of monodisperse LiFePO4 micro hollow spheres as high performance cathode material for lithium ion batteries.

    PubMed

    Yang, Shiliu; Hu, Mingjun; Xi, Liujiang; Ma, Ruguang; Dong, Yucheng; Chung, C Y

    2013-09-25

    A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl2·4H2O as the Fe(2+) source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the LFP micro hollow spheres have a quite uniform size of ~1 μm consisting of aggregated nanoparticles. The influences of solvent and Fe(2+) source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe(2+) ions was firstly proposed on the basis of the X-ray powder diffraction (XRD) transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coat a uniform carbon layer ~3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101, and even 72 mAh g(-1) at 0.1, 1, 5, 20, and 50 C, respectively. It could also maintain 80% of the initial discharge capacity after cycling for 2000 times at 20 C.

  16. High power Nb-doped LiFePO4 Li-ion battery cathodes; pilot-scale synthesis and electrochemical properties

    NASA Astrophysics Data System (ADS)

    Johnson, Ian D.; Blagovidova, Ekaterina; Dingwall, Paul A.; Brett, Dan J. L.; Shearing, Paul R.; Darr, Jawwad A.

    2016-09-01

    High power, phase-pure Nb-doped LiFePO4 (LFP) nanoparticles are synthesised using a pilot-scale continuous hydrothermal flow synthesis process (production rate of 6 kg per day) in the range 0.01-2.00 at% Nb with respect to total transition metal content. EDS analysis suggests that Nb is homogeneously distributed throughout the structure. The addition of fructose as a reagent in the hydrothermal flow process, followed by a post synthesis heat-treatment, affords a continuous graphitic carbon coating on the particle surfaces. Electrochemical testing reveals that cycling performance improves with increasing dopant concentration, up to a maximum of 1.0 at% Nb, for which point a specific capacity of 110 mAh g-1 is obtained at 10 C (6 min for the charge or discharge). This is an excellent result for a high power cathode LFP based material, particularly when considering the synthesis was performed on a large pilot-scale apparatus.

  17. Soft-contact conductive carbon enabling depolarization of LiFePO4 cathodes to enhance both capacity and rate performances of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Ren, Wenju; Wang, Kai; Yang, Jinlong; Tan, Rui; Hu, Jiangtao; Guo, Hua; Duan, Yandong; Zheng, Jiaxin; Lin, Yuan; Pan, Feng

    2016-11-01

    Conductive nanocarbons generally are used as the electronic conductive additives to contact with active materials to generate conductive network for electrodes of commercial Li-ion batteries (LIBs). A typical of LiFePO4 (LFP), which has been widely used as cathode material for LIBs with low electronic conductivity, needs higher quantity of conductive nanocarbons to enhance the performance for cathode electrodes. In this work, we systematically studied three types of conductive nanocarbons and related performances in the LFP electrodes, and classify them as hard/soft-contact conductive carbon (named as H/SCC), respectively, according to their crystallite size, surface graphite-defect, specific surface area and porous structure, in which SCC can generate much larger contact area with active nano-particles of cathode materials than that of HCC. It is found that LFP nanocrystals wrapped in SCC networks perform significantly enhanced both capacity and rate performance than that in HCC. Combined experiments with multiphysics simulation, the mechanism is that LFP nanoparticles embedded in SCC with large contact area enable to generate higher depolarized effects with a relatively uniform current density vector (is) and lithium flux vector (NLi) than that in HCC. This discovery will guide us to how to design LIBs by selective using conductive carbon for high-performance LIBs.

  18. On the complex ageing characteristics of high-power LiFePO4/graphite battery cells cycled with high charge and discharge currents

    NASA Astrophysics Data System (ADS)

    Groot, Jens; Swierczynski, Maciej; Stan, Ana Irina; Kær, Søren Knudsen

    2015-07-01

    Li-ion batteries are known to undergo complex ageing processes, where the operating conditions have a profound and non-linear effect on both calendar life and cycle life. This is especially a challenge for the automotive industry, where the requirements on product lifetime and reliability are demanding. The aim of the present work is to quantify the ageing in terms of capacity fade and impedance growth as a function of operating conditions typical to high-power automotive applications; high charge and discharge rate, elevated temperatures and wide state-of-charge windows. The cycle life of 34 power-optimised LiFePO4/graphite cells was quantified by testing with charge and discharge rates between 1 and 4C-rate, temperatures between +23 °C and +53 °C, and a depth-of-discharge of either 100% or 60%. Although all cells show similar ageing pattern in general, the cycle life and the impedance growth is remarkably different for the tested cases. In addition, it is concluded that high charging rates, high temperatures or intensive cycling do not always lead to a shorter cycle life. One specifically interesting finding is that the combination of 1C-rate discharge in combination with 3.75C-rate charging was found to degrade the tested cells more rapidly than a symmetric cycle with 3.75C-rate in both directions.

  19. Porous α-Fe2O3 nanostructures and their lithium storage properties as full cell configuration against LiFePO4

    NASA Astrophysics Data System (ADS)

    Veluri, P. S.; Shaligram, A.; Mitra, S.

    2015-10-01

    A two step approach for synthesis of porous α-Fe2O3 nanostructures has been realized via polyol method by complexing iron oxalate with ethylene glycol. Crystalline Fe2O3 samples with different porosities are obtained by calcination of Fe-Ethylene glycol complex at various temperatures. The as-prepared porous Fe2O3 structures exhibit promising lithium storage performance at high current rates. It is observed that the calcination temperature and the resultant porosity have a significant effect on capacity and cycling stability. Samples calcined at high temperature (600 °C) demonstrates stable cycle life with capacity retention of 1077 mAh g-1 at 500 mA g-1 current rate after 50 charge-discharge cycles. Samples calcined at temperatures of 500 and 600 °C display stable cycle life and high rate capability with reversible capacity of 930 mAh g-1 and 688 mAh g-1 at 5 A g-1, respectively. Impregnation of electrodes with electrolyte before cell fabrication shows enhanced electrochemical performance. The viability of Fe2O3 porous nanostructures as prospective anode material examined against commercial LiFePO4 cathode shows promising electrochemical performance.

  20. Online state of charge and model parameters estimation of the LiFePO4 battery in electric vehicles using multiple adaptive forgetting factors recursive least-squares

    NASA Astrophysics Data System (ADS)

    Duong, Van-Huan; Bastawrous, Hany Ayad; Lim, KaiChin; See, Khay Wai; Zhang, Peng; Dou, Shi Xue

    2015-11-01

    This paper deals with the contradiction between simplicity and accuracy of the LiFePO4 battery states estimation in the electric vehicles (EVs) battery management system (BMS). State of charge (SOC) and state of health (SOH) are normally obtained from estimating the open circuit voltage (OCV) and the internal resistance of the equivalent electrical circuit model of the battery, respectively. The difficulties of the parameters estimation arise from their complicated variations and different dynamics which require sophisticated algorithms to simultaneously estimate multiple parameters. This, however, demands heavy computation resources. In this paper, we propose a novel technique which employs a simplified model and multiple adaptive forgetting factors recursive least-squares (MAFF-RLS) estimation to provide capability to accurately capture the real-time variations and the different dynamics of the parameters whilst the simplicity in computation is still retained. The validity of the proposed method is verified through two standard driving cycles, namely Urban Dynamometer Driving Schedule and the New European Driving Cycle. The proposed method yields experimental results that not only estimated the SOC with an absolute error of less than 2.8% but also characterized the battery model parameters accurately.

  1. Entropy change effects on the thermal behavior of a LiFePO4/graphite lithium-ion cell at different states of charge

    NASA Astrophysics Data System (ADS)

    Jalkanen, K.; Aho, T.; Vuorilehto, K.

    2013-12-01

    The enthalpy and entropy changes in a commercial lithium-ion cell were studied by using potentiometric measurements. The experiments were done on the full cell and individually on its electrode materials, LiFePO4 and artificial graphite. The graphite electrode entropy change follows the amount of intercalated lithium, whereas the LFP electrode entropy change is independent of the lithium content. The full cell entropy change behavior can be concluded to originate from the graphite electrode. For the states of charge between 30 and 75%, the full cell entropy change is positive in the discharge direction, causing the cell to absorb heat. Thus when low discharge currents are used, this entropy effect dominates over the irreversible, heat producing losses, and as a result the cell cools down. In the charge direction the entropy change has the same absolute value but is negative in sign. Because of this, the cell produces extra heat in addition to the irreversible heat production, and thus warms up. These phenomena were confirmed in a calorimetric experiment. The thermal behavior results can be utilized in designing the battery pack cooling system and in choosing favorable states of charge for the battery cycling.

  2. Effects of Laser Energy and Wavelength on the Analysis of LiFePO4 Using Laser Assisted Atom Probe Tomography

    SciTech Connect

    Santhanagopalan, Dhamodaran; Schreiber, Daniel K.; Perea, Daniel E.; Martens, Rich; Janssen, Yuri; Kalifah, Peter; Meng, Ying S.

    2015-01-21

    The effects of laser wavelength (355 nm and 532 nm) and laser pulse energy on the quantitative accuracy of atom probe tomography (APT) examinations of LiFePO4 (LFP) are considered. A systematic investigation of ultraviolet (UV, 355 nm) and green (532 nm) laser assisted APT of LFP has revealed distinctly different behaviors. With the use of UV laser the major issue was identified as the preferential loss of oxygen (up to 10 at. %) while other elements (Li, Fe and P) were observed to be close to nominal ratios. Lowering the laser energy per pulse to 1 pJ increased the observed oxygen concentration to near its correct stoichiometry and was well correlated with systematically higher concentrations of 16O2+ ions. This observation supports the premise that lower laser energies lead to a higher probability of oxygen molecule ionization. Conversely, at higher laser energies the resultant lower effective electric field reduces the probability of oxygen molecule ionization. Green laser assisted field evaporation led to the selective loss of Li (~50% deficiency) and correct ratios of the remaining elements, including the oxygen concentration. The loss of Li is explained by selective dc evaporation of lithium between laser pulses and relatively negligible oxygen loss as neutrals during green-laser pulsing. Lastly, plotting of multihit events on a Saxey plot for the straight-flight path data (green laser only) revealed a surprising dynamic recombination process for some molecular ions mid-flight.

  3. Fast‐Rate Capable Electrode Material with Higher Energy Density than LiFePO4: 4.2V LiVPO4F Synthesized by Scalable Single‐Step Solid‐State Reaction

    PubMed Central

    Kim, Minkyung; Lee, Seongsu

    2015-01-01

    Use of compounds that contain fluorine (F) as electrode materials in lithium ion batteries has been considered, but synthesizing single‐phase samples of these compounds is a difficult task. Here, it is demonstrated that a simple scalable single‐step solid‐state process with additional fluorine source can obtain highly pure LiVPO4F. The resulting material with submicron particles achieves very high rate capability ≈100 mAh g−1 at 60 C‐rate (1‐min discharge) and even at 200 C‐rate (18 s discharge). It retains superior capacity, ≈120 mAh g−1 at 10 C charge/10 C discharge rate (6‐min) for 500 cycles with >95% retention efficiency. Furthermore, LiVPO4F shows low polarization even at high rates leading to higher operating potential >3.45 V (≈3.6 V at 60 C‐rate), so it achieves high energy density. It is demonstrated for the first time that highly pure LiVPO4F can achieve high power capability comparable to LiFePO4 and much higher energy density (≈521 Wh g−1 at 20 C‐rate) than LiFePO4 even without nanostructured particles. LiVPO4F can be a real substitute of LiFePO4.

  4. Kimberlite Ascent: Insights from Olivine

    NASA Astrophysics Data System (ADS)

    Brett, C.; Russell, K.

    2009-05-01

    Olivine is ubiquitous in both extrusive and intrusive kimberlite deposits worldwide. Within kimberlite, it is mainly present as xenocrysts derived from the disaggregation of mantle-derived peridotitic xenoliths. Many textural and chemical features within the mantle-derived olivine xenocrysts result from post entrainment processes. On that basis, these features record physical and chemical changes attending kimberlite ascent and can be used to elucidate the transport and eruption of kimberlite magma. Our textural study of kimberlitic olivine is based on intrusive and pyroclastic kimberlite from the Diavik kimberlite cluster and from the Igwisi Hills kimberlitic lava flows. Based on these observations and the physical and chemical properties of olivine we derive a relative sequence of textural events. Textural features include: sealed cracks, healed cracks, phases trapping in cracks, rounded grains, overgrowths and phase trapping in overgrowths. These features record processes that operate in kimberlite during ascent, and from these features we create a summary model for kimberlite ascent: -- Olivine is incorporated into kimberlitic melts in peridotitic mantle xenoliths continuously during ascent. Xenolith incorporation is focused at the crack tip where the stress regime is highest. -- Shortly after the incorporation of these xenocrysts the tensile strength of the xenoliths is reached at a maximum of 2 km from its source. Disaggregation of mantle xenoliths (producing xenocrysts) is facilitated by expansion of the minerals within the xenoliths causing intra-crystal slip (i.e. along grain boundaries). -- Continued decompression causes olivine to also break in tension approximately 20 km from source. The void space produced by the failure of the crystals (inter-crystal cracks) is filled with melt and crystals consisting of primary carbonate (high-Sr), chromite and spinel crystals. The carbonate later crystallizes to produce sealed fractures. -- Mechanical rounding of

  5. Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

    PubMed

    Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

    2015-12-14

    In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Néel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J⊥) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4. PMID:26548581

  6. Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

    PubMed

    Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

    2015-12-14

    In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Néel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J⊥) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4.

  7. The characteristic of carbon-coated LiFePO4 as cathode material for lithium ion battery synthesized by sol-gel process in one step heating and varied pH

    NASA Astrophysics Data System (ADS)

    Triwibowo, J.; Yuniarti, E.; Suharyadi, E.

    2014-09-01

    This research has been done on the synthesis of carbon coated LiFePO4 through sol-gel process. Carbon layer serves for improving electronic conductivity, while the variation of pH in the sol-gel process is intended to obtain the morphology of the material that may improve battery performance. LiFePO4/C precursors are Li2CO3, NH4H2PO4 and FeC2O4˙H2O and citric acid. In the synthesis process, consisting of a colloidal suspension FeC2O4˙H2O and distilled water mixed with a colloidal suspension consisting of NH4H2PO4, Li2CO3, and distilled water. Variations addition of citric acid is used to control the pH of the gel formed by mixing two colloidal suspensions. Sol in this study had a pH of 5, 5.4 and 5.8. The obtained wet gel is further dried in the oven and then sintered at a temperature 700°C for 10 hours. The resulting material is further characterized by XRD to determine the phases formed. The resulting powder morphology is observed through SEM. Specific surface area of the powder was tested by BET, while the electronic conductivity characterized with EIS.

  8. Origin of olivine at Copernicus

    NASA Astrophysics Data System (ADS)

    Pieters, Carle M.; Wilhelms, Don E.

    1985-02-01

    The central peaks of Copernicus are among the few lunar areas where near-infrared telescopic reflectance spectra indicate extensive exposures of olivine. Other parts of Copernicus crater and ejecta, which were derived from highland units in the upper parts Of the target site, contain only low-Ca pyroxene as a mafic mineral. The exposure of compositionally distinct layers including the presence of extensive olivine may result from penetration to an anomalously deep layer of the crust or to the lunar mantle. We suggest that the Procellarum basin and the younger, superposed Insularum basin have provided access to these normally deep-seated crustal or mantle materials by thinning the upper crustal material early in lunar history. The occurrences of olivine in portions of the compositionally heterogeneous Aristarchus Region, in a related geologic setting, may be due to the same sequence of early events.

  9. Origin of olivine at Copernicus

    NASA Astrophysics Data System (ADS)

    Pieters, C. M.; Wilhelms, D. E.

    1985-02-01

    The central peaks of Copernicus are among the few lunar areas where near-infrared telescopic reflectance spectra indicate extensive exposures of olivine. Other parts of Copernicus crater and ejecta, which were derived from highland units in the upper parts of the target site, contain only low-Ca pyroxene as a mafic mineral. The exposure of compositionally distinct layers including the presence of extensive olivine may result from penetration to an anomalously deep layer of the crust or to the lunar mantle. It is suggested that the Procellarum basin and the younger, superposed Insularum basin have provided access to these normally deep-seated crustal or mantle materials by thinning the upper crustal material early in lunar history. The occurrences of olivine in portions of the compositionally heterogeneous Aristarchus Region, in a related geologic setting, may be due to the same sequence of early events.

  10. Origin of olivine at Copernicus

    NASA Technical Reports Server (NTRS)

    Pieters, C. M.; Wilhelms, D. E.

    1985-01-01

    The central peaks of Copernicus are among the few lunar areas where near-infrared telescopic reflectance spectra indicate extensive exposures of olivine. Other parts of Copernicus crater and ejecta, which were derived from highland units in the upper parts of the target site, contain only low-Ca pyroxene as a mafic mineral. The exposure of compositionally distinct layers including the presence of extensive olivine may result from penetration to an anomalously deep layer of the crust or to the lunar mantle. It is suggested that the Procellarum basin and the younger, superposed Insularum basin have provided access to these normally deep-seated crustal or mantle materials by thinning the upper crustal material early in lunar history. The occurrences of olivine in portions of the compositionally heterogeneous Aristarchus Region, in a related geologic setting, may be due to the same sequence of early events.

  11. Performance and kinetics of LiFePO4-carbon bi-material electrodes for hybrid devices: A comparative study between activated carbon and multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Varzi, Alberto; Ramirez-Castro, Claudia; Balducci, Andrea; Passerini, Stefano

    2015-01-01

    Activated Carbon (AC) and multi-walled carbon nanotubes (CNT) are investigated as components of LiFePO4 (LFP)-based bi-material electrodes for hybrid devices. Firstly, the influence of their different morphological and porosimetric characteristics is correlated to the electrochemical performance. Furthermore, kinetic aspects are carefully studied (by means of galvanostatic cycling and cyclic voltammetry), in order to address the processes which determine the power performance. The results indicate that, independently from the carbon, under high current loads the electrode kinetics are limited by the transport of reactant to the LFP particles. In such conditions CNT allow, better than AC, rapid electrons and Li+ ions flow through the open network established in the electrode, thus enabling superior high rate performance, especially during pulsed operation.

  12. Supernova olivine from cometary dust.

    PubMed

    Messenger, Scott; Keller, Lindsay P; Lauretta, Dante S

    2005-07-29

    An interplanetary dust particle contains a submicrometer crystalline silicate aggregate of probable supernova origin. The grain has a pronounced enrichment in 18O/16O (13 times the solar value) and depletions in 17O/16O (one-third solar) and 29Si/28Si (<0.8 times solar), indicative of formation from a type II supernova. The aggregate contains olivine (forsterite 83) grains <100 nanometers in size, with microstructures that are consistent with minimal thermal alteration. This unusually iron-rich olivine grain could have formed by equilibrium condensation from cooling supernova ejecta if several different nucleosynthetic zones mixed in the proper proportions. The supernova grain is also partially encased in nitrogen-15-rich organic matter that likely formed in a presolar cold molecular cloud.

  13. Supernova olivine from cometary dust

    NASA Technical Reports Server (NTRS)

    Messenger, Scott; Keller, Lindsay P.; Lauretta, Dante S.

    2005-01-01

    An interplanetary dust particle contains a submicrometer crystalline silicate aggregate of probable supernova origin. The grain has a pronounced enrichment in 18O/16O (13 times the solar value) and depletions in 17O/16O (one-third solar) and 29Si/28Si (<0.8 times solar), indicative of formation from a type II supernova. The aggregate contains olivine (forsterite 83) grains <100 nanometers in size, with microstructures that are consistent with minimal thermal alteration. This unusually iron-rich olivine grain could have formed by equilibrium condensation from cooling supernova ejecta if several different nucleosynthetic zones mixed in the proper proportions. The supernova grain is also partially encased in nitrogen-15-rich organic matter that likely formed in a presolar cold molecular cloud.

  14. High-Performance Olivine NaFePO4 Microsphere Cathode Synthesized by Aqueous Electrochemical Displacement Method for Sodium Ion Batteries.

    PubMed

    Fang, Yongjin; Liu, Qi; Xiao, Lifen; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

    2015-08-19

    Olivine NaFePO4/C microsphere cathode is prepared by a facile aqueous electrochemical displacement method from LiFePO4/C precursor. The NaFePO4/C cathode shows a high discharge capacity of 111 mAh g(-1), excellent cycling stability with 90% capacity retention over 240 cycles at 0.1 C, and high rate capacity (46 mAh g(-1) at 2 C). The excellent electrochemical performance demonstrates that the aqueous electrochemical displacement method is an effective and promising way to prepare NaFePO4/C material for Na-based energy storage applications. Moreover, the Na2/3FePO4 intermediate is observed for the first time during the Na intercalation process through conventional electrochemical techniques, corroborating an identical two-step phase transition reaction both upon Na intercalation and deintercalation processes. The clarification of the electrochemical reaction mechanism of olivine NaFePO4 could inspire more attention on the investigation of this material for Na ion batteries.

  15. Influence of lithium vacancies on the polaronic transport in olivine phosphate structure

    NASA Astrophysics Data System (ADS)

    Murugavel, Sevi; Sharma, Monika; Shahid, Raza

    2016-01-01

    Intercalation and deintercalation of lithium ions in cathode materials are of principal to the operation of current rechargeable lithium ion batteries. The performance of lithium ion batteries highly relies on the active cathode material which includes cell potential, power/energy density, capacity, etc. An important issue in this class of material is to resolve the factors governing the electron and ion transport in olivine phosphate structure. In this class of material, there is still an open debate on the mechanism of charge transport including both polarons and lithium ions. On the one hand, this is due to the large disparity between the experimental results and the theoretical model predictions. On the other hand, this is also due to the lack of precise experimental measurement without any parasitic phases in a given cathode material. Here, we present the polaronic conduction in lithiated triphylite LiFePO4 (LFP) and delithiated heterosite FePO4 (FP) by means of broadband ac impedance spectroscopy over wide range temperatures and frequency. It is found that the LFP phase possess two orders of higher polaronic conductivity than FP phase despite having similar mobility of polarons in both phases. We show that the differences in the polaronic conductivity of two phases are due to the significant differences in concentration of polarons. It is found that the formation energy of polarons in individual phases is mainly determined by the corresponding defect state associated with it. The temperature dependent dc conductivity has been analyzed within the framework of Mott model of polaronic conduction and explored the origin of polaronic conduction mechanism in this class of material.

  16. Unveil the Chemistry of Olivine FePO4 as Magnesium Battery Cathode.

    PubMed

    Zhang, Ruigang; Ling, Chen

    2016-07-20

    Despite growing interest in magnesium batteries, it is still a challenge to find a cathode that fulfills requirements such as high capacity and good cyclability. Because of their positions in the periodic table and the similar ionic sizes of lithium and magnesium, it was naturally postulated that a classical intercalation-type Li-ion battery cathode may also accommodate the intercalation of Mg. On the contrary, many Li-ion battery cathodes performed very poorly in Mg cells, although the mechanism behind such phenomena is still unclear. Here we provide first-hand evidence about the chemistry of olivine FePO4 as Mg battery cathode using a combined theoretical and experimental approach. Although LiFePO4 is a commercial cathode with extraordinary good performance in Li-ion batteries, the measured capacity of FePO4 in nonaqueous Mg cell was only ∼13 mAh/g. Density functional theory calculations predicted sufficient mobility of Mg(2+) in FePO4 lattice to support the insertion of Mg at a reasonable rate, suggesting the poor performance cannot be simply attributed to the limitation of Mg(2+) diffusion. Instead, the recorded low capacity was the result of surface amorphorization that prohibited the electrochemical reaction from penetrating deeply into the bulk phase. The amorphorization had a thermodynamic origin from the instability of intercalated product, which was predicted from DFT calculations and supported by the failure to synthesize magnesiated FePO4 in the solid state reaction route. These results highlighted the importance of a thermodynamically preferred intercalation in order to achieve successful Mg battery cathode.

  17. Unveil the Chemistry of Olivine FePO4 as Magnesium Battery Cathode.

    PubMed

    Zhang, Ruigang; Ling, Chen

    2016-07-20

    Despite growing interest in magnesium batteries, it is still a challenge to find a cathode that fulfills requirements such as high capacity and good cyclability. Because of their positions in the periodic table and the similar ionic sizes of lithium and magnesium, it was naturally postulated that a classical intercalation-type Li-ion battery cathode may also accommodate the intercalation of Mg. On the contrary, many Li-ion battery cathodes performed very poorly in Mg cells, although the mechanism behind such phenomena is still unclear. Here we provide first-hand evidence about the chemistry of olivine FePO4 as Mg battery cathode using a combined theoretical and experimental approach. Although LiFePO4 is a commercial cathode with extraordinary good performance in Li-ion batteries, the measured capacity of FePO4 in nonaqueous Mg cell was only ∼13 mAh/g. Density functional theory calculations predicted sufficient mobility of Mg(2+) in FePO4 lattice to support the insertion of Mg at a reasonable rate, suggesting the poor performance cannot be simply attributed to the limitation of Mg(2+) diffusion. Instead, the recorded low capacity was the result of surface amorphorization that prohibited the electrochemical reaction from penetrating deeply into the bulk phase. The amorphorization had a thermodynamic origin from the instability of intercalated product, which was predicted from DFT calculations and supported by the failure to synthesize magnesiated FePO4 in the solid state reaction route. These results highlighted the importance of a thermodynamically preferred intercalation in order to achieve successful Mg battery cathode. PMID:27355741

  18. Multiple origins for olivine at Copernicus crater

    NASA Astrophysics Data System (ADS)

    Dhingra, Deepak; Pieters, Carle M.; Head, James W.

    2015-06-01

    Multiple origins for olivine-bearing lithologies at Copernicus crater are recognized based on integrated analysis of data from Chandrayaan-1 Moon Mineralogy Mapper (M3), Lunar Reconnaissance Orbiter (LRO) Narrow Angle Camera (NAC) and Kaguya Terrain Camera (TC). We report the diverse morphological and spectral character of previously known olivine-bearing exposures as well as the new olivine occurrences identified in this study. Prominent albedo differences exist between olivine-bearing exposures in the central peaks and a northern wall unit (the latter being ∼40% darker). The low-albedo wall unit occurs as a linear mantling deposit and is interpreted to be of impact melt origin, in contrast with the largely unmodified nature of olivine-bearing peaks. Small and localized occurrences of olivine-bearing lithology have also been identified on the impact melt-rich floor, representing a third geologic setting (apart from crater wall and peaks). Recent remote sensing missions have identified olivine-bearing exposures around lunar basins (e.g. Yamamoto et al., 2010; Pieters et al., 2011; Kramer et al., 2013) and at other craters (e.g. Sun and Li, 2014), renewing strong interest in its origin and provenance. A direct mantle exposure has commonly been suggested in this regard. Our detailed observations of the morphological and spectral diversity in the olivine-bearing exposures at Copernicus have provided critical constraints on their origin and source regions, emphasizing multiple formation mechanisms. These findings directly impact the interpretation of olivine exposures elsewhere on the Moon. Olivine can occur in diverse environments including an impact melt origin, and therefore it is unlikely for all olivine exposures to be direct mantle occurrences as has generally been suggested.

  19. The ascent of kimberlite: Insights from olivine

    NASA Astrophysics Data System (ADS)

    Brett, R. C.; Russell, J. K.; Andrews, G. D. M.; Jones, T. J.

    2015-08-01

    Olivine xenocrysts are ubiquitous in kimberlite deposits worldwide and derive from the disaggregation of mantle-derived peridotitic xenoliths. Here, we provide descriptions of textural features in xenocrystic olivine from kimberlite deposits at the Diavik Diamond Mine, Canada and at Igwisi Hills volcano, Tanzania. We establish a relative sequence of textural events recorded by olivine during magma ascent through the cratonic mantle lithosphere, including: xenolith disaggregation, decompression fracturing expressed as mineral- and fluid-inclusion-rich sealed and healed cracks, grain size and shape modification by chemical dissolution and abrasion, late-stage crystallization of overgrowths on olivine xenocrysts, and lastly, mechanical milling and rounding of the olivine cargo prior to emplacement. Ascent through the lithosphere operates as a "kimberlite factory" wherein progressive upward dyke propagation of the initial carbonatitic melt fractures the overlying mantle to entrain and disaggregate mantle xenoliths. Preferential assimilation of orthopyroxene (Opx) xenocrysts by the silica-undersaturated carbonatitic melt leads to deep-seated exsolution of CO2-rich fluid generating buoyancy and supporting rapid ascent. Concomitant dissolution of olivine produces irregular-shaped relict grains preserved as cores to most kimberlitic olivine. Multiple generations of decompression cracks in olivine provide evidence for a progression in ambient fluid compositions (e.g., from carbonatitic to silicic) during ascent. Numerical modelling predicts tensile failure of xenoliths (disaggregation) and olivine (cracks) over ascent distances of 2-7 km and 15-25 km, respectively, at velocities of 0.1 to >4 m s-1. Efficient assimilation of Opx during ascent results in a silica-enriched, olivine-saturated kimberlitic melt (i.e. SiO2 >20 wt.%) that crystallizes overgrowths on partially digested and abraded olivine xenocrysts. Olivine saturation is constrained to occur at pressures <1 GPa; an

  20. Aligned olivine in the Springwater pallasite

    NASA Astrophysics Data System (ADS)

    Fowler-Gerace, Neva A.; Tait, Kimberly T.; Moser, Desmond E.; Barker, Ivan; Tian, Bob Y.

    2016-06-01

    The mechanism by which olivine grains became embedded within iron-nickel alloy in pallasite meteorites continues to be a matter of scientific debate. Geochemical and textural observations have failed to fully elucidate the origin and history of the olivine crystals; however, little research attention has been devoted to their crystallographic orientations within the metal matrix. Using electron backscatter diffraction, we have collected crystallographic orientation data for 296 crystals within ˜65 cm2 sample surface from Springwater. Though no global crystallographic preferred orientation exists, very low misorientations are observed among [100] axes of olivine crystals within specific texturally defined domains. Combined with a thorough characterization of large-scale Springwater textures, the definitively nonrandom spatial distribution of olivine orientations provides clues regarding the nature of the olivine's initial formation environment as well as the sequence of events subsequent to metal incorporation.

  1. Mineralogical Study of Reddish Olivine in Dhofar 307 Lunar Meteorite: Comparison with Brown Olivine in Martian Meteorites

    NASA Astrophysics Data System (ADS)

    Takenouchi, A.; Mikouchi, T.

    2016-08-01

    We compared reddish olivine in Dhofar 307 lunar meteorite to brown olivine in martian meteorites and indicate a possibility of its shock origin. This result suggests that olivine darkening may have widely occurred on the surface of large bodies.

  2. Crystallization kinetics of olivine-phyric shergottites

    NASA Astrophysics Data System (ADS)

    Ennis, Megan E.; McSween, Harry Y.

    2014-08-01

    Crystal size distribution (CSD) and spatial distribution pattern (SDP) analyses are applied to the early crystallizing phases, olivine and pyroxene, in olivine-phyric shergottites (Elephant moraine [EET] 79001A, Dar al Gani [DaG] 476, and dhofar [Dho] 019) from each sampling locality inferred from Mars ejection ages. Trace element zonation patterns (P and Cr) in olivine are also used to characterize the crystallization history of these Martian basalts. Previously reported 2-D CSDs for these meteorites are re-evaluated using a newer stereographically corrected methodology. Kinks in the olivine CSD plots suggest several populations that crystallized under different conditions. CSDs for pyroxene in DaG 476 and EET 79001A reveal single populations that grew under steady-state conditions; pyroxenes in Dho 019 were too intergrown for CSD analysis. Magma chamber residence times of several days for small grains to several months for olivine megacrysts are calculated using the CSD slopes and growth rates inferred from previous experimental data. Phosphorus imaging in olivines in DaG 476 and Dho 019 indicate rapid growth of skeletal, sector-zoned, or patchy cores, probably in response to delayed nucleation, followed by slow growth, and finally rapid dendritic growth with back-filling to form oscillatory zoning in rims. SPD analyses indicate that olivine and pyroxene crystals grew or accumulated in clusters rather than as randomly distributed grains. These data reveal complex solidification histories for Martian basalts, and are generally consistent with the formation at depth of olivine megacryst cores, which were entrained in ascending magmas that crystallized pyroxenes, small olivines, and oscillatory rims on megacrysts.

  3. Experimental Study of Olivine-rich Troctolites

    NASA Astrophysics Data System (ADS)

    Mu, S.; Faul, U.

    2014-12-01

    This experimental study is designed to complement field observations of olivine-rich troctolites in ophiolites and from mid-ocean ridges. The olivine-rich troctolites are characterized by high volume proportion of olivine with interstitial plagioclase and clinopyroxene. Typically the clinopyroxene occurs in the form of few large, poikilitic grains. The primary purpose of this study is to investigate the effects of cooling process on the geometry of the interstitial phases (clinopyroxene and plagioclase). Experiments are conducted in a piston cylinder apparatus by first annealing olivine plus a basaltic melt with a composition designed to be in equilibrium with four phases at ~ 1 GPa and 1250ºC. Initially, we anneal the olivine-basalt aggregates at 1350 °C and 0.7 GPa for one week to produce a steady state microstructure. At this temperature only olivine and minor opx are present as crystalline phases. We then cool the samples over two weeks below their solidus temperature, following different protocols. The post-run samples are sectioned, polished, and imaged at high resolution and analyzed by using a field emission SEM. Initial observations show that under certain conditions clinopyroxene nucleates distributed throughout the aggregate at many sites, forming relatively small, rounded to near euhedral grains. Under certain conditions few cpx grains nucleate and grow with a poikilitic shape, partially or fully enclosing olivine grains, as is observed in natural samples. As for partially molten aggregates quenched form the annealing temperature, the microstructure will be characterized by tracing phase boundaries on screen by using ImageJ software. The geometry of the interstitial phases will be quantified by determining the grain boundary wetness, in this case the ratio of the length of polyphase to single phase (olivine-olivine) boundaries. Compositional data will also be used to study the change in major element compositions before and after the cooling process.

  4. Olivine-dominated asteroids: Mineralogy and origin

    NASA Astrophysics Data System (ADS)

    Sanchez, Juan A.; Reddy, Vishnu; Kelley, Michael S.; Cloutis, Edward A.; Bottke, William F.; Nesvorný, David; Lucas, Michael P.; Hardersen, Paul S.; Gaffey, Michael J.; Abell, Paul A.; Corre, Lucille Le

    2014-01-01

    Olivine-dominated asteroids are a rare type of objects formed either in nebular processes or through magmatic differentiation. The analysis of meteorite samples suggest that at least 100 parent bodies in the main belt experienced partial or complete melting and differentiation before being disrupted. However, only a few olivine-dominated asteroids, representative of the mantle of disrupted differentiated bodies, are known to exist. Due to the paucity of these objects in the main belt their origin and evolution have been a matter of great debate over the years. In this work we present a detailed mineralogical analysis of twelve olivine-dominated asteroids. We have obtained near-infrared (NIR) spectra (0.7-2.4 μm) of asteroids (246) Asporina, (289) Nenetta, (446) Aeternitas, (863) Benkoela, (4125) Lew Allen and (4490) Bamberry. Observations were conducted with the Infrared Telescope Facility (IRTF) on Mauna Kea, Hawai'i. This sample was complemented with spectra of six other olivine-dominated asteroids including (354) Eleonora, (984) Gretia, (1951) Lick, (2501) Lohja, (3819) Robinson and (5261) Eureka obtained by previous workers. Within our sample we distinguish two classes, one that we call monomineralic-olivine asteroids, which are those whose spectra only exhibit the 1 μm feature, and another referred to as olivine-rich asteroids, whose spectra exhibit the 1 μm feature and a weak (Band II depth ˜4%) 2 μm feature. For the monomineralic-olivine asteroids the olivine chemistry was found to range from ˜Fo49 to Fo70, consistent with the values measured for brachinites and R chondrites. In the case of the olivine-rich asteroids we determined their olivine and low-Ca pyroxene abundance using a new set of spectral calibrations derived from the analysis of R chondrites spectra. We found that the olivine abundance for these asteroids varies from 0.68 to 0.93, while the fraction of low-Ca pyroxene to total pyroxene ranges from 0.6 to 0.9. A search for dynamical

  5. Exsolved kirschsteinite in angrite LEW86010 olivine

    NASA Technical Reports Server (NTRS)

    Mikouchi, Takashi; Takeda, Hiroshi; Mori, Hiroshi; Miyamoto, Masamichi; Mckay, Gordon

    1993-01-01

    Mineralogy of kirschsteinite exsolution in olivine from Antarctic meteorite LEW86010 has been studied by single crustal X-ray diffraction technique. The LEW86010 olivine crystals have exsolution lamellae of kirschteinite about 15 microns wide. Determination of crystallographic orientation of exsolved kirschsteinite in an olivine grain has been made. Weak reflections of exsolved kirschsteinite share common crystallographic orientation with the host olivine. The cell dimensions of the exsolved phase (a - 4.87 plus or minus 0.05A, b - 11.14 plus or minus 0.10A, c - 6.36 plus or minus 0.05A) and intensities were in well accord with those of kirschsteinite previously reported. Oriented section perpendicular to the a axis shows exsolution lamellae in two directions parallel to (031) and (031). The lamellae are up to 10 microns in width and spacings between them are usually 50-100 microns.

  6. Olivine in Almahata Sitta - Curiouser and Curiouser

    NASA Technical Reports Server (NTRS)

    Zolensky, M. E.; Herrin, J.; Mikouchi, T.; Satake, W.; Kurihara, T.; Sandford, S. A.; Milam, S. N.; Hagiya, K.; Ohsumi, K.; Friedrich, J. M.; Jeniskens, P.; Shaddad, M. H.; Le, L.; Robinson, G. A.

    2010-01-01

    Almahata Sitta (hereafter Alma) is an anomalous, polymict ureilite. Anomalous features include low abundance of olivine, large compositional range of silicates, high abundance and large size of pores, crystalline pore wall linings, and overall finegrained texture. Tomography suggests the presence of foliation, which is known from other ureilites. Alma pyroxenes and their interpretation are discussed in two companion abstracts. In this abstract we discuss the composition of olivine in Alma, which is indicative of the complexity of this meteorite.

  7. An Amoeboid Olivine Aggregate in LEW 85300

    NASA Technical Reports Server (NTRS)

    Komatsu, M. D.; Yamaguchi, A.; Fagan, T. J.; Zolensky, M. E.; Shiran, N.; Mikouchi, T.

    2016-01-01

    Amoeboid Olivine aggregates (AOAs) are irregularly shaped objects commonly observed in carbonaceous chondrites. Because they are composed of fine-grained olivine and Ca-Al-rich minerals, they are sensitive indicators for nebular process and parent body alteration of their parent bodies. Recently an AOA was found in a carbonaceous clast in polymict eucrite LEW 85300. The bulk major element composition of the clast matrix in LEW 85300 suggests a relation to CM, CO and CV chondrites, whereas bulk clast trace and major element compositions do not match any carbonaceous chondrite, suggesting they have a unique origin. Here we characterize the mineralogy of AOA in LEW 85300 and discuss the origin of the carbonaceous clasts. Results and Discussion: The AOA is located in an impact melt vein. Half of the aggregate shows recrystallization textures (euhedral pyroxene and molten metal/FeS) due to impact melting, but the remaining part preserves the original texture. The AOA is composed of olivine, FeS and Mg,Al-phyllosilicate. Individual olivine grains measure 1-8 microns, with Fe-rich rims, probably due to impact heating. Olivines in the AOA are highly forsteritic (Fo95-99), indicating that the AOA escaped thermal metamorphism [4]. Although no LIME (Low-Fe, Mn-Enriched) olivine is observed, forsterite composition and the coexistence of Mg,Al-phyllosilicate suggest that the AOA is similar to those in the Bali-type oxidized CV (CVoxB) and CR chondrites. However, it should be noted that fayalitic olivine, which commonly occurs in CVoxB AOA, is not observed in this AOA. Also, the smaller grain size (<8 microns) of olivine suggests they may be related to CM or CO chondrites. Therefore, we cannot exclude the possibility that the AOA originated from a unique carbonaceous chondrite.

  8. Exsolved Ferromagnesian Olivine: Why Only in Divnoe?

    NASA Astrophysics Data System (ADS)

    Petaev, M. I.

    1995-09-01

    Recently Petaev and Brearley [1] showed that lamellar structure in olivine grains in the Divnoe meteorite was produced by the low-temperature exsolution of primary homogeneous grains. Exsolved olivine in Divnoe is in accordance with the thermodynamic model of olivine solid solution of [2], which predicts a miscibility gap in ferromagnesian olivines below ~340 degrees C within a compositional range that widens with decreasing temperature. Experiments on the coexistence of olivines having a range of compositions with aqueous solutions of (Fe,Mg)Cl2 [3] suggest that exsolution in ferromagnesian olivines could occur even at temperatures as high as ~400 - 450 degrees C. However, [1] remains the only observation of exsolution in natural olivines so far. This means either that (1) the exsolution in Divnoe olivine is unique, or (2) olivine grains in other slowly cooled coarse-grained rocks has not been studied closely enough to detect them. This work attempts to clarify the issue. Olivine grains from selected meteorites (Springwater pallasite, Lowitz mesosiderite, ALHA 84025 brachinite, Gorlovka H3-4 chondrite and Krymka L3 chondrite, and the Calcalong Creek lunar meteorite) and terrestrial rocks (San Carlos forsterite and Rockport fayalite) were studied by EPMA using the same equipment and technique as in [1]. Among meteorites, pallasites and mesosiderites are known to have slowest cooling rates at low temperatures. Olivines in the Springwater pallasite (Fa18) [4] and the Lowitz mesosiderite (Fa15-37) [5] are compositionally comparable with that of Divnoe (Fa23-29) [1], and it was expected that exsolved olivine grains would be found there. Olivines from other samples were studied for comparison. No lamellar structure was observed in BSE images of the olivine grains studied. The variations of Fa contents in olivine grains from all samples but Springwater and Lowitz meteorites display no regular pattern, and are basically within the 2sigma uncertainty range (+/-0.2 mole

  9. Drastically Enhanced High-Rate Performance of Carbon-Coated LiFePO4 Nanorods Using a Green Chemical Vapor Deposition (CVD) Method for Lithium Ion Battery: A Selective Carbon Coating Process.

    PubMed

    Tian, Ruiyuan; Liu, Haiqiang; Jiang, Yi; Chen, Jiankun; Tan, Xinghua; Liu, Guangyao; Zhang, Lina; Gu, Xiaohua; Guo, Yanjun; Wang, Hanfu; Sun, Lianfeng; Chu, Weiguo

    2015-06-01

    Application of LiFePO4 (LFP) to large current power supplies is greatly hindered by its poor electrical conductivity (10(-9) S cm(-1)) and sluggish Li+ transport. Carbon coating is considered to be necessary for improving its interparticle electronic conductivity and thus electrochemical performance. Here, we proposed a novel, green, low cost and controllable CVD approach using solid glucose as carbon source which can be extended to most cathode and anode materials in need of carbon coating. Hydrothermally synthesized LFP nanorods with optimized thickness of carbon coated by this recipe are shown to have superb high-rate performance, high energy, and power densities, as well as long high-rate cycle lifetime. For 200 C (18s) charge and discharge, the discharge capacity and voltage are 89.69 mAh g(-1) and 3.030 V, respectively, and the energy and power densities are 271.80 Wh kg(-1) and 54.36 kW kg(-1), respectively. The capacity retention of 93.0%, and the energy and power density retention of 93.6% after 500 cycles at 100 C were achieved. Compared to the conventional carbon coating through direct mixing with glucose (or other organic substances) followed by annealing (DMGA), the carbon phase coated using this CVD recipe is of higher quality and better uniformity. Undoubtedly, this approach enhances significantly the electrochemical performance of high power LFP and thus broadens greatly the prospect of its applications to large current power supplies such as electric and hybrid electric vehicles.

  10. Raman spectra of shocked minerals. I. Olivine

    SciTech Connect

    Heymann, D.; Celucci, T.A.

    1988-12-01

    The Raman spectra of olivine contained in a chip of the Twin Sisters Peak (Washington) dunite shocked to 22.2 GPa is shown to be identical to that of unshocked olivine in the same rock. The Raman spectra of powder of the rock shocked to 20.1 GPa and of chips shocked to 59.5 GPa and 60.7 GPa display strong and broad low-frequency features with crests at 475/cm, 556/cm, and 572/cm, and broad high-frequency features near 1100/cm. It is suggested that these features are due to the formation of olivine glass with a considerable degree of three-dimensional Si-O-Si linkage having scattered domains of greatly variable grain size, internal structure, and chemical composition. 54 references.

  11. Raman spectra of shocked minerals. I - Olivine

    NASA Technical Reports Server (NTRS)

    Heymann, D.; Celucci, T. A.

    1988-01-01

    The Raman spectra of olivine contained in a chip of the Twin Sisters Peak (Washington) dunite shocked to 22.2 GPa is shown to be identical to that of unshocked olivine in the same rock. The Raman spectra of powder of the rock shocked to 20.1 GPa and of chips shocked to 59.5 GPa and 60.7 GPa display strong and broad low-frequency features with crests at 475/cm, 556/cm, and 572/cm, and broad high-frequency features near 1100/cm. It is suggested that these features are due to the formation of olivine glass with a considerable degree of three-dimensional Si-O-Si linkage having scattered domains of greatly variable grain size, internal structure, and chemical composition.

  12. Shock-produced olivine glass - First observation

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.; Ahrens, T. J.; Lally, J. S.; Nord, G. L., Jr.; Christie, J. M.; Heuer, A. H.

    1977-01-01

    Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, /Mg(0.88)Fe(0.12)/2SiO4, recovered from peak pressures of about 56 billion pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation of olivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 billion pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.

  13. Nebular history of amoeboid olivine aggregates

    NASA Astrophysics Data System (ADS)

    Sugiura, N.; Petaev, M. I.; Kimura, M.; Miyazaki, A.; Hiyagon, H.

    2009-05-01

    Minor element (Ca, Cr, and Mn) concentrations in amoeboid olivine aggregates (AOAs) from primitive chondrites were measured and compared with those predicted by equilibrium condensation in the solar nebula. CaO concentrations in forsterite are low, particularly in porous aggregates. A plausible explanation appears that an equilibrium Ca activity was not maintained during the olivine condensation. CaO and MnO in forsterite are negatively correlated, with CaO being higher in compact aggregates. This suggests that the compact aggregates formed either by a prolonged reheating of the porous aggregates or by condensation and aggregation of forsterite during a very slow cooling in the nebula.

  14. Direct Shear of Olivine Single Crystals

    NASA Astrophysics Data System (ADS)

    Tielke, Jacob; Zimmerman, Mark; Kohlstedt, David

    2016-04-01

    Knowledge of the strength of individual dislocation slip systems in olivine is fundamental to understanding the flow behavior and the development of lattice-preferred orientation in olivine-rich rocks. The most direct measurements of the strengths of individual slip systems are from triaxial compression experiments on olivine single crystals. However, such experiments only allow for determination of flow laws for two of the four dominate slip systems in olivine. In order to measure the strengths of the (001)[100] and (100)[001] slip systems independently, we performed deformation experiments on single crystals of San Carlos olivine in a direct shear geometry. Experiments were carried out at temperatures of 1000° to 1300°C, a confining pressure of 300 MPa, shear stresses of 60 to 334 MPa, and resultant shear strain rates of 7.4 x 10‑6 to 6.7 x 10‑4 s‑1. At high-temperature (≥1200°C) and low-stress (≤200 MPa) conditions, the strain rate of crystals oriented for direct shear on either the (001)[100] or the (100)[001] slip system follows a power law relationship with stress, whereas at lower temperatures and higher stresses, strain rate depends exponentially on stress. The flow laws derived from the mechanical data in this study are consistent with a transition from the operation of a climb-controlled dislocation mechanism during power-law creep to the operation of a glide-controlled dislocation mechanism during exponential creep. In the climb-controlled regime, crystals oriented for shear on the (001)[100] slip system are weaker than crystals orientated for shear on the (100)[001] slip system. In contrast, in the glide-controlled regime the opposite is observed. Extrapolation of flow laws determined for crystals sheared in orientations favorable for slip on these two slip systems to upper mantle conditions reveals that the (001)[100] slip system is weaker at temperatures and stresses that are typical of the asthenospheric mantle, whereas the (100

  15. A Chemical Model of Micrometeorite Impact into Olivine

    NASA Technical Reports Server (NTRS)

    Sheffer, A. A.; Melosh, H. J.

    2005-01-01

    Laboratory simulations of space weathering using laser irradiation have been successful in reproducing space weathering characteristics such as the reduction of olivine to form nanophase iron particles. However, the chemistry of the reduction of Fe2+ in olivine to Fe metal has not been fully explored. We present a thermodynamic model of olivine undergoing post-impact cooling and decompression.

  16. Transmission electron microscopy of subsolidus oxidation and weathering of olivine

    USGS Publications Warehouse

    Banfield, J.F.; Veblen, D.R.; Jones, B.F.

    1990-01-01

    Olivine crystals in basaltic andesites which crop out in the Abert Rim, south-central Oregon have been studied by high-resolution and analytical transmission electron microscopy. The observations reveal three distinct assemblages of alteration products that seem to correspond to three episodes of olivine oxidation. The olivine crystals contain rare, dense arrays of coherently intergrown Ti-free magnetite and inclusions of a phase inferred to be amorphous silica. We interpret this first assemblage to be the product of an early subsolidus oxidation event in the lava. The second olivine alteration assemblage contains complex ordered intergrowths on (001) of forsterite-rich olivine and laihunite (distorted olivine structure with Fe3+ charge balanced by vacancies). Based on experimental results for laihunite synthesis (Kondoh et al. 1985), these intergrowths probably formed by olivine oxidation between 400 and 800??C. The third episode of alteration involves the destruction of olivine by low-temperature hydrothermal alteration and weathering. Elongate etch-pits and channels in the margins of fresh olivine crystals contain semi-oriented bands of smectite. Olivine weathers to smectite and hematite, and subsequently to arrays of oriented hematite crystals. The textures resemble those reported by Eggleton (1984) and Smith et al. (1987). We find no evidence for a metastable phase intermediate between olivine and smectite ("M" - Eggleton 1984). The presence of laihunite exerts a strong control on the geometry of olivine weathering. Single laihunite layers and laihunite-forsteritic olivine intergrowths increase the resistance of crystals to weathering. Preferential development of channels between laihunite layers occurs where growth of laihunite produced compositional variations in olivine, rather than where coherency-strain is associated with laihunite-olivine interfaces. ?? 1990 Springer-Verlag.

  17. Oriented crystallographic textures of olivine in quenched silicate melt spherules

    NASA Astrophysics Data System (ADS)

    Isobe, H.

    2015-12-01

    Olivine is one of the most common minerals in the planetary materials including solid Earth and chondritic meteorites. Olivine crystals show characteristic textures in chondrules and micrometeorites (MMs) depending on heating and cooling histories, especially in extraordinary quick cooling rates. We have constructed a fine particle free fall apparatus in a high temperature furnace and carried out crystallization experiments of fine particles with quick heating and quenching (Isobe and Gondo, 2013). The falling particles in the furnace can reach 1400 degrees C within 2 seconds, keep above 1400 degrees C more than 1 second, and are quenched within 1 second. Run products from olivine particles show various textures depending on proportions of three kinds of starting materials in the particles. Fayalite particles melt completely and form barred olivine-like spherules with low pyramid structures on the surface. Dendritic olivine crystals with regulated crystallographic orientation are developed in melted particles. Surface texture of melted particles may be affected by the dendritic olivine crystals grown in the spherules. Oriented dendrites of magnetite also occur between olivine crystals. The texture of oriented dendrite of olivine with tiny magnetite is quite similar to natural cosmic spherules (CSs). In the completely melted spherules, barred olivine-like structures can be seen. Due to extraordinary high cooling rate up to 2×10^6 degrees C/hour and degrees of supercooling, olivine bars show chained structure of H-shaped or hourglass shaped units which are distinctive characteristics for quick growth of olivine in quenching. In spite of quite short period of crystal growth processes, chained olivine aligns parallel bars in the almost entire spherule. Nucleation of barred olivine crystals may be initiated at surface of spherules. Starting points of olivine growth can be seen as peaks on surface of the spherules. The crystallographic textures of olivine develop

  18. Water loss from olivine hosted melt inclusions

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Provost, A.; Schiano, P.; Cluzel, N.

    2009-12-01

    Water content in melt inclusions has long been used as an important index for the water content of the hosting magma. However, many studies have shown that post-entrapment diffusive re-equilibration can affect the water content of melt inclusions. This process must be considered when using melt inclusions to infer water content of the hosting magma. Theoretical model on the diffusive re-equilibration between melt inclusions and external melts showed that the re-equilibration rate depends on the diffusivity of the re-equilibrating species in the host mineral, the partition coefficient of this species between the host mineral and melt, and the geometry of the melt inclusion and host mineral. The water diffusivity in olivine and water partition coefficient between melt and olivine have been measured by recent studies, therefore the diffusive re-equilibration model can be tested by experiments. In this study, we carried out in-situ Fourier transform infrared spectroscopy (FTIR) measurements on the water content of olivine hosted melt inclusions at high temperatures. Initial water content of the melt inclusions is about 4 wt%. A heating stage system is combined with a microscope FTIR and the absorption spectrum through the olivine and melt inclusion is repeatedly measured. Although the absorption band at around 3540 cm-1 has not be calibrated at high temperatures, it is assumed that the absorbance is linearly related to the total water concentration in the melt inclusion, and the relative water content can be inferred. Cautions have been exercised to maintain a consistent measurement spot such that the thickness of the melt inclusion within the beam path did not change significantly during each experiment. Oxygen fugacity in the heating stage is controlled by Zr purified Ar gas to be about 7 logarithm units below the QFM buffer and about 1 logarithm unit above the QIF buffer at 1473 K. Preliminary results showed that at 1430 and 1581 K, the total water content of the

  19. Diffusive behavior in LiMPO4 with M=Fe, Co, Ni probed by muon-spin relaxation

    NASA Astrophysics Data System (ADS)

    Sugiyama, Jun; Nozaki, Hiroshi; Harada, Masashi; Kamazawa, Kazuya; Ikedo, Yutaka; Miyake, Yasuhiro; Ofer, Oren; Månsson, Martin; Ansaldo, Eduardo J.; Chow, Kim H.; Kobayashi, Genki; Kanno, Ryoji

    2012-02-01

    In order to study the diffusive nature of lithium transition-metal phospho-olivines, we measured muon-spin relaxation (μ+SR) spectra for the polycrystalline LiMPO4 samples with M=Mn, Fe, Co, or Ni in the temperature range between 50 and 500 K. The μ+SR spectra under zero applied field are strongly affected by the magnetic moments of the 3d electrons in the M2+ ions so that, for LiMnPO4, it was difficult to detect the relaxation change caused by the diffusion due to the large Mn2+(S=5/2) moments. However, diffusive behavior was clearly observed via the relaxation due to nuclear dipolar fields above ˜150 K for LiFePO4, LiCoPO4, and LiNiPO4 as S decreased from 2 to 1. From the temperature dependence of the nuclear field fluctuation rate, self-diffusion coefficients of Li+ ions (DLi) at 300 K and its activation energy (Ea) were estimated, respectively, as ˜3.6(2)×10-10 cm2/s and Ea=0.10(2) eV for LiFePO4, ˜1.6(1)×10-10 cm2/s and Ea=0.10(1) eV for LiCoPO4, and ˜2.7(4)×10-10 cm2/s and Ea=0.17(2) eV for LiNiPO4, assuming that the diffusing Li+ ions jump between the regular site and interstitial sites.

  20. Shock-produced olivine glass: First observation

    USGS Publications Warehouse

    Jeanloz, R.; Ahrens, T.J.; Lally, J.S.; Nord, G.L.; Christie, J.M.; Heuer, A.H.

    1977-01-01

    Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, (Mg0.88Fe 0.12SiO4 recovered from peak pressures of about 56 ?? 109 pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation ofolivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 ?? 109 pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.

  1. Trace-Element Diffusion Coefficients in Olivine

    NASA Astrophysics Data System (ADS)

    Spandler, C.; O'Neill, H. S.

    2006-12-01

    We have undertaken chemical diffusion experiments at 1300°C to determine both crystal/melt partition coefficients and diffusion coefficients for a wide range of trace elements in forsteritic olivine. Experiments were conducted at 1 atm under controlled fO2 for up to 25 days using synthetic melts made to a composition in equilibrium with olivine for major elements, and doped with selected trace elements. The melt was put into a 5 mm diameter cylindrical hole in gem quality San Carlos olivine crystals drilled paralell to the a axis. Diffusion profiles were obtained both for trace elements that were added to the starting material and diffuse into the olivine, and also for several trace elements present at natural abundances in the olivine that diffuse out. The profiles were measured across sections perpendicular to crystal/melt boundary at a variety of crystallographic orientations (confirmed by EBSD) by laser-ablation ICP-MS. A thin laser slit oriented parallel to the crystal/melt interface was traversed from the melt through the crystal. Element concentrations were fitted to the diffusion equation to obtain both diffusion coefficients and concentrations at the crystal/melt interface, and hence partition coefficients. Calculated diffusivities for many trace elements (Ca, REE, Y, Sc, V, Cr, Ni, Co, Mn, Na, Li, Be, Ti) are relatively fast (D = 10-16 to 10^{-13 m2/s at 1300°C). The diffusion of Li in olivine (approx. D = 10^{-15} m2/s) is only slightly slower than REEs and similar to divalent cations, in good agreement with inferences from zoning profiles in natural olivine [1]. This rate is considerably slower than for plagioclase and clinopyroxene [2], a result which has important implications for interpreting Li isotopic data from mantle-derived rocks. The fastest diffusing trace element we observe is Be. Applying our diffusion and partition coefficients to the model of Qin et al. [3], we calculate that the REEs of olivine-hosted melt inclusions in the mantle will

  2. Dislocation Microstructures in Experimentally Deformed wet Olivine

    NASA Astrophysics Data System (ADS)

    Sharp, T. G.; Jung, H.; Karato, S.

    2002-12-01

    Seismic anisotropy in the upper mantle is generally considered to be the result of lattice preferred orientations (LPOs) of olivine as a result of mantle flow. Therefore seismic anisotropy in the upper mantle can be used to probe fabrics and therefore flow directions. Jung and Karato (2001) have demonstrated that fabrics developed in experimentally deformed olivine are dependent on H2O fugacity and stress. Fabric type C, which develops at moderate experimental stresses and high H2O fugacities, has [001] subparallel to the slip direction and (100) subparallel to the shear plane. Fabric type B, which develops at high stresses and high H2O fugacities has [001] subparallel to the slip direction and (010) subparallel to the shear plane. To investigate the role of H2O in olivine fabric transitions, we are using high-resolution and conventional transmission electron microscopy (HRTEM and TEM) to characterize the dislocation microstructures and core structures in experimentally deformed samples of Fabric types B and C. Initial results for Fabric type C (sample JK11 of Jung and Karato, 2001) show a dominance of mixed-character and screw dislocations with Burgers vectors b = [001]. This Burgers vector, combined with the (100) being subparallel to the shear plane, is consistent with the (100)[001] slip system being dominant in the C-type fabric. This slip system, which is of minor importance in dry olivine, may be favored in wet samples by changes in the dislocation core structure. We are currently using HRTEM imaging to characterize the dislocation core structures in deformed samples with type C and type B fabrics.

  3. Investigation of sodium insertion–extraction in olivine Na x FePO 4 (0 ≤ x ≤ 1) using first-principles calculations

    SciTech Connect

    Saracibar, A.; Carrasco, J.; Saurel, D.; Galceran, M.; Acebedo, B.; Anne, H.; Lepoitevin, M.; Rojo, T.; Casas Cabanas, M.

    2016-01-01

    Olivine NaFePO4 has recently attracted the attention of the scientific community as a promising cathode material for Na-ion batteries. In this work we combine density functional theory (DFT) calculations and high resolution synchrotron X-ray diffraction (HRXRD) experiments to study the phase stability of NaxFePO4 along the whole range of sodium compositions (0 ≤ x ≤ 1). DFT calculations reveal the existence of two intermediate structures governing the phase stability at x = 2/3 and x = 5/6. This is in contrast to isostructural LiFePO4, which is a broadly used cathode in Li-ion batteries. Na2/3FePO4 and Na5/6FePO4 ground states both align vacancies diagonally within the ab plane, coupled to a Fe2+/Fe3+ alignment. HRXRD data for NaxFePO4 (2/3 < x < 1) materials show common superstructure reflections up to x = 5/6 within the studied compositions. The computed intercalation voltage profile shows a voltage difference of 0.16 V between NaFePO4 and Na2/3FePO4 in agreement with the voltage discontinuity observed experimentally during electrochemical insertion.

  4. Exploring exogenic sources for the olivine on Asteroid (4) Vesta

    NASA Astrophysics Data System (ADS)

    Le Corre, Lucille; Reddy, Vishnu; Sanchez, Juan A.; Dunn, Tasha; Cloutis, Edward A.; Izawa, Matthew R. M.; Mann, Paul; Nathues, Andreas

    2015-09-01

    The detection of olivine on Vesta is interesting because it may provide critical insights into planetary differentiation early in our Solar System's history. Ground-based and Hubble Space Telescope (HST) observations of Asteroid (4) Vesta have suggested the presence of olivine on the surface. These observations were reinforced by the discovery of olivine-rich HED meteorites from Vesta in recent years. However, analysis of data from NASA's Dawn spacecraft has shown that this "olivine-bearing unit" is actually impact melt in the ejecta of Oppia crater. The lack of widespread mantle olivine, exposed during the formation of the 19 km deep Rheasilvia basin on Vesta's South Pole, further complicated this picture. Ammannito et al. (Ammannito, E. et al. [2013a]. Nature 504, 122-125) reported the discovery of local scale olivine-rich units in the form of excavated material from the mantle using the Visible and InfraRed spectrometer (VIR) on Dawn. These sites are concentrated in the walls and ejecta of craters Arruntia (10.5 km in diameter) and Bellicia (41.7 km in diameter), located in the northern hemisphere, 350-430 km from Rheasilvia basin's rim. Here we explore alternative sources for the olivine in the northern hemisphere of Vesta by reanalyzing the data from the VIR instrument using laboratory spectral measurements of meteorites. Our rationale for using the published dataset was to bypass calibration issues and ensure a consistent dataset between the two studies. Our analysis of the VIR data shows that while the interpretation of their spectra as an olivine-rich unit is correct, the nature and origin of that olivine could be more complicated. We suggest that these olivine exposures could also be explained by the delivery of olivine-rich exogenic material. This hypothesis is supported by meteoritical evidence in the form of exogenic xenoliths containing significant amount of olivine in some of the HED meteorites from Vesta. Previous laboratory work on HEDs show that

  5. Water and Carbon Dioxide Adsorption at Olivine Surfaces

    SciTech Connect

    Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

    2013-11-14

    Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbon dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.

  6. Diffusive Fractionation of Lithium Isotopes in Olivine

    NASA Astrophysics Data System (ADS)

    Homolova, V.; Richter, F. M.; Watson, E. B.; Chaussidon, M.

    2014-12-01

    Systematic lithium isotope variations along concentration gradients found in olivine and pyroxene grains from terrestrial, lunar and martian rocks have been attributed to diffusive isotopic fractionation [Beck et al., 2006; Tang et al., 2007]. In some cases, these isotopic excursions are so large that a single grain may display isotopic variability that spans almost the entire range of documented terrestrial values [Jeffcoate et al., 2007]. In this study, we present the results of experiments to examine diffusive isotopic fractionation of lithium in olivine. The experiments comprised crystallographically oriented slabs of San Carlos olivine juxtaposed with either spodumene powder or a lithium rich pyroxene crystal. Experiments were conducted at 1 GPa and 0.1MPa over a temperature range of 1000 to 1125⁰C. Oxygen fugacity in the 0.1MPa experiments was controlled using the wustite-magnetite and nickel-nickel oxide solid buffer assemblages. Lithium concentrations generally decrease smoothly away from the edges of the grains; however, experiments involving diffusion parallel to the a-axis consistently show peculiar wavy or segmented concentration profiles. Lithium diffusivity parallel to the c-axis is on the order of 1E-14m2/s at 1100⁰C. The diffusivity parallel to the c-axis is more than an order of magnitude faster than diffusion parallel to the b-axis and correlates positively with oxygen fugacity. The lithium isotopic composition, δ7Li = 1000‰ * ((δ7Lisample- δ7Ligrain center)/ δ7Ligrain center), shows a decrease away from the edge of the grain to a minimum value (up to 70‰ lighter) and then an abrupt increase back to the initial isotopic composition of the olivine grain. This isotopic profile is similar to those found in natural grains and an experimental study on diffusive fractionation of lithium isotopes in pyroxene [Richter et al., 2014]. Results from the present study are modeled using the approach of Dohmen et al. [2010], which assumes lithium

  7. Vaporization Studies of Olivine via Knudsen Effusion Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Costa, G. C. C.; Jacobson, N. S.

    2014-01-01

    Olivine is the major mineral in the Earth's upper mantle occurring predominantly in igneous rocks and has been identified in meteorites, asteroids, the Moon and Mars. Among many other important applications in planetary and materials sciences, the thermodynamic properties of vapor species from olivine are crucial as input parameters in computational modelling of the atmospheres of hot, rocky exoplanets (lava planets). There are several weight loss studies of olivine vaporization in the literature and one Knudsen Effusion Mass Spectrometry (KEMS) study. In this study, we examine a forsterite-rich olivine (93% forsterite and 7% fayalite, Fo93Fa7) with KEMS to further understand its vaporization and thermodynamic properties.

  8. Discovery of Olivine in the Nili Fossae Region of Mars

    USGS Publications Warehouse

    Hoefen, T.M.; Clark, R.N.; Bandfield, J.L.; Smith, M.D.; Pearl, J.C.; Christensen, P.R.

    2003-01-01

    We have detected a 30,000-square-kilometer area rich in olivine in the Nili Fossae region of Mars. Nili Fossae has been interpreted as a complex of grabens and fractures related to the formation of the Isidis impact basin. We propose that post-impact faulting of this area has exposed subsurface layers rich in olivine. Linear mixture analysis of Thermal Emission Spectrometer spectra shows surface exposures of 30% olivine, where the composition of the olivine ranges from Fo30 to Fo70.

  9. A scanning electron microscope study of olivine crystal surfaces

    NASA Technical Reports Server (NTRS)

    Olsen, E. J.; Grossman, L.

    1974-01-01

    SEM photographs were taken of euhedral olivine grains from the Murchison C2 chondrite and several terrestrial and lunar occurrences. In general, the crystal faces of the meteorite grains are rough and uneven, with irregular growth patterns. They are very similar to crystal faces on terrestrial olivine grains that formed by sublimation from a vapor phase. They are very different from the relatively smooth and featureless surfaces of magmatic olivine crystals that precipitated from igneous melts. Qualitatively, the surface morphology of the crystal supports the contention that many euhedral crystals of olivine in C2 meteorites condensed from a gas phase.

  10. Electronic Properties of LiFePO4 and Li doped LiFePO4

    SciTech Connect

    Allen, J.L.; Zhuang, G.V.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

    2006-05-31

    LiFePO{sub 4} has several potential advantages in comparison to the transition metal oxide cathode materials used in commercial lithium-ion batteries. However, its low intrinsic electronic conductivity ({approx} 10{sup -9} S/cm) is problematic. We report here a study by soft x-ray absorption/emission spectroscopy of the electronic properties of undoped LiFePO{sub 4} and Li-doped LiFePO{sub 4} in which Li{sup +} ions are substituted for Fe{sup 2+} ions in an attempt to increase the intrinsic electronic conductivity. The conductivities of the Li{sub 1+x}Fe{sub 1-x}PO{sub 4} samples were, however, essentially unchanged from that of the undoped LiFePO{sub 4}. Nonetheless, evidence for changing the electronic properties of LiFePO{sub 4} by doping with excess Li+ was observed by the XAS/XES spectroscopy. New pre-edge features the O-1s XAS spectrum of Li{sub 1.05}Fe{sub 0.95}PO4 is a direct indication that the charge compensation for substitution of Fe{sup 2+} by Li{sup +} resides in the unoccupied O-2p orbitals. A charge transfer (CT) excitation was also observed in the doped material implying that the unoccupied O-2p orbitals created by doping are strongly hybridized with unoccupied Fe-3d orbitals of neighboring sites. However, the strong covalent bonding within the (PO{sub 4}){sup 3-} anions and the large separation of the Fe cations means that the charge created by doping is not delocalized in the manner of electrons or holes in a semiconductor.

  11. Anisotropy of electrical conductivity in dry olivine

    SciTech Connect

    Du Frane, W L; Roberts, J J; Toffelmier, D A; Tyburczy, J A

    2005-04-13

    [1] The electrical conductivity ({sigma}) was measured for a single crystal of San Carlos olivine (Fo{sub 89.1}) for all three principal orientations over oxygen fugacities 10{sup -7} < fO{sub 2} < 10{sup 1} Pa at 1100, 1200, and 1300 C. Fe-doped Pt electrodes were used in conjunction with a conservative range of fO{sub 2}, T, and time to reduce Fe loss resulting in data that is {approx}0.15 log units higher in conductivity than previous studies. At 1200 C and fO{sub 2} = 10{sup -1} Pa, {sigma}{sub [100]} = 10{sup -2.27} S/m, {sigma}{sub [010]} = 10{sup -2.49} S/m, {sigma}{sub [001]} = 10{sup -2.40} S/m. The dependences of {sigma} on T and fO{sub 2} have been simultaneously modeled with undifferentiated mixed conduction of small polarons and Mg vacancies to obtain steady-state fO{sub 2}-independent activation energies: Ea{sub [100]} = 0.32 eV, Ea{sub [010]} = 0.56 eV, Ea{sub [001]} = 0.71 eV. A single crystal of dry olivine would provide a maximum of {approx}10{sup 0.4} S/m azimuthal {sigma} contrast for T < 1500 C. The anisotropic results are combined to create an isotropic model with Ea = 0.53 eV.

  12. Mineralogical Comparison of Olivine in Shergottites and A Shocked L Chondrite: Implications for Shock Histories of Brown Olivine

    NASA Technical Reports Server (NTRS)

    Takenouchi, A.; Mikouchi, T.; Yamaguchi, A.; Zolensky, M. E.

    2015-01-01

    Most Martian meteorites are heavily shocked, exhibiting numerous shock features, for example undulatory extinction of olivine and pyroxene, the presence of diaplectic glass ("maskelynite") and the formation of shock melt. Among these shock features, olivine darkening ("brown" olivine) is unique in Martian meteorites because no other meteorite group shows such a feature. Although the presence of brown olivine in shergottites was reported thirty years ago, detailed observation by TEM has not been performed until the NWA 2737 chassignite was discovered, whose olivine is darkened, being completely black in hand specimen. Fe metal nano-particles were found in NWA 2737 olivine which are considered to have been formed by olivine reduction during heavy shock. Subsequently, magnetite nano-particles were also found in other Martian meteorites and the coexistence of Fe metal and magnetite nano-particles was reported in the NWA 1950 shergottite and some Fe metal nano-particles were mantled by magnetite. Therefore, the formation process of nano-particles seems to be complex. Because "brown" olivine is unique to Martian meteorites, they have a potential to constrain their shock conditions. In order to better understand the shock history of Martian meteorites, we compared olivine in several shergottites with that in a highly-shocked L chondrite which contains ringwoodite.

  13. Fast grain growth of olivine in liquid Fe-S and the formation of pallasites with rounded olivine grains

    NASA Astrophysics Data System (ADS)

    Solferino, Giulio F. D.; Golabek, Gregor J.; Nimmo, Francis; Schmidt, Max W.

    2015-08-01

    Despite their relatively simple mineralogical composition (olivine + Fe-Ni metal + FeS ± pyroxene), the origin of pallasite meteorites remains debated. It has been suggested that catastrophic mixing of olivine fragments with Fe-(Ni)-S followed by various degrees of annealing could explain pallasites bearing solely or prevalently fragmented or rounded olivines. In order to verify this hypothesis, and to quantify the grain growth rate of olivine in a liquid metal matrix, we performed a series of annealing experiments on natural olivine plus synthetic Fe-S mixtures. The best explanation for the observed olivine grain size distributions (GSD) of the experiments are dominant Ostwald ripening for small grains followed by random grain boundary migration for larger grains. Our results indicate that olivine grain growth in molten Fe-S is significantly faster than in solid, sulphur-free metal. We used the experimentally determined grain growth law to model the coarsening of olivine surrounded by Fe-S melt in a 100-600 km radius planetesimal. In this model, an impact is responsible for the mixing of olivine and Fe-(Ni)-S. Numerical models suggest that annealing at depths of up to 50 km allow for (i) average grain sizes consistent with the observed rounded olivine in pallasites, (ii) a remnant magnetisation of Fe-Ni olivine inclusions as measured in natural pallasites and (iii) for the metallographic cooling rates derived from Fe-Ni in pallasites. This conclusion is valid even if the impact occurs several millions of years after the differentiation of the target body was completed.

  14. Olivine in the Southern Isidis Basin

    NASA Technical Reports Server (NTRS)

    2007-01-01

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) took this observation of the transition region between Libya Montes and the Isidis Basin on Mars at 17:16 UTC (12:16 p.m. EST) on January 2, 2007, near 3.6 degrees north latitude, 84.1 degrees east longitude. The image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 18 meters (60 feet) across. The image is about 11 kilometers (7 miles) wide at its narrowest point.

    The Isidis Basin resulted from of a gigantic impact on the surface of Mars early in the planet's history. The southern rim, where this target is located, is a region of complex geology and part of the planetary dichotomy boundary that separates the older southern highlands from the lower, younger northern plains. The image on the left was constructed from three visible wavelengths (RGB: 0.71, 0.60, 0.53 microns) and is a close approximation of how the surface would appear to the human eye. The image on the right was constructed from three infrared wavelengths (RGB: 2.49, 1.52, 1.08 microns) chosen to highlight variations in the mineralogy of the area. Of interest is that features in this image not only differ in color, but also in texture and morphology. The gray areas absorb similarly at all wavelengths used in this image, but display absorptions at other wavelengths related to the iron- and magesium-rich mineral pyroxene. The reddest areas absorb strongly at the wavelengths used for green and blue, which is attributable to another iron- and magesium-rich mineral, olivine. The brownish areas show subdued mineral absorptions and could represent some type of mixture between the other two materials. The presence of the mineral olivine is particularly interesting because olivine easily weathers to other minerals; thus, its presence indicates either the lack of weathering in this region or relatively recent exposure.

    CRISM's mission: Find the spectral fingerprints of aqueous and hydrothermal

  15. Did Ordinary Chondrite Impactors Deliver Olivine to Vesta?

    NASA Astrophysics Data System (ADS)

    Le Corre, Lucille; Reddy, Vishnu; Sanchez, Juan A.; Cloutis, Edward A.; Izawa, Matthew R.; Mann, Paul

    2014-11-01

    Ground-based and Hubble Space Telescope observations of asteroid Vesta suggested the presence of olivine. However, subsequent analysis of data from NASA’s Dawn mission proved that this “olivine-bearing unit”, identified as Oppia crater and its ejecta blanket, was composed of HED impact melt rather than olivine. The lack of widespread olivine in the 19 km deep Rheasilvia basin on the South Pole suggests that the crust-mantle boundary was not breached during the formation of the basin, and that Vesta’s crust is thicker than originally anticipated. Recently, local-scale olivine units have been reported in the walls and ejecta of two craters, Arruntia and Bellicia, located in the northern hemisphere of Vesta, 350-430 km from the Rheasilvia basin (Ammannito et al., 2013). These units were interpreted as exposed plutons by Clenet et al. (2014) rather than of mantle origin excavated during the formation of the Rheasilvia basin. We explored alternative sources for these olivine-rich units by reanalyzing the data published by Ammannito et al. (2013). Our mineralogical analysis gives olivine abundance between 70-80 vol.% consistent with those obtained previously (>60%). The pyroxene ferrosilite content and olivine abundance of the olivine-rich units are similar to ordinary chondrites. Meteoritic evidence suggests contamination of HEDs by several ordinary chondrite impactors including H, L and LL chondrites. This includes howardite JaH 556, which contains ~20 vol.% H chondrite material mixed with HED impact melt. Based on the non-diagnostic curve match and detailed mineralogical analysis using diagnostic spectral band parameters, we conclude that the olivine units in the northern hemisphere of Vesta could be explained by the delivery of exogenic H/L chondrite material rather than being a product of planetary differentiation.

  16. Boron, beryllium, and lithium, partitioning in olivine

    SciTech Connect

    Neroda, Elizabeth

    1996-05-01

    A one atmosphere experimental study was performed to determine the mineral/melt partition coefficients for B, Be, and Li in forsteritic olivine. Two compositions were chosen along the 1350{degrees}C isotherm, 1b (Fo{sub 17.3} Ab{sub 82.7} An{sub 0} by weight) and 8c (Fo{sub 30} Ab{sub 23.3} An{sub 47.8}, by weight) were then combined in equal amounts to form a composition was doped with 25ppm Li, B, Yb, Nb, Zr, Sr, and Hf, 50ppm Sm, and 100ppm Be, Nd, Ce, and Rb. Electron and ion microprobe analyses showed that the olivine crystals and surrounding glasses were homogeneous with respect to major and trace elements. Partition coefficients calculated from these analyses are as follows: 1b: D{sub B} = 4.41 ({+-} 2.3) E-03, D{sub Be} = 2.86 ({+-} 0.45) E-03, D{sub Li} = 1.54 ({+-} 0.21) E-01, 50/50: D{sub B} = 2.86 ({+-} 0.5) E-03, D{sub Be} = 2.07 ({+-} 0.09) E-03, D{sub Li} = 1.51 ({+-} 0.18) E-01, 8c: D{sub B} = 6.05 ({+-} 1.5) E-03, D{sub Be} = 1.81 ({+-} 0.03) E-03, D{sub Li} = 1.31 ({+-} 0.09) E-01. The results of this study will combined with similar data for other minerals as part of a larger study to understand the partitioning behavior of B, Be, and Li in melting of the upper mantle at subduction zones.

  17. Cotectic proportions of olivine and spinel in olivine-tholeiitic basalt and evaluation of pre-eruptive processes

    USGS Publications Warehouse

    Roeder, P.; Gofton, E.; Thornber, C.

    2006-01-01

    The volume %, distribution, texture and composition of coexisting olivine, Cr-spinel and glass has been determined in quenched lava samples from Hawaii, Iceland and mid-oceanic ridges. The volume ratio of olivine to spinel varies from 60 to 2800 and samples with >0.02% spinel have a volume ratio of olivine to spinel of approximately 100. A plot of wt % MgO vs ppm Cr for natural and experimental basaltic glasses suggests that the general trend of the glasses can be explained by the crystallization of a cotectic ratio of olivine to spinel of about 100. One group of samples has an olivine to spinel ratio of approximately 100, with skeletal olivine phenocrysts and small (100 ??m) spinel crystals that show evidence of two stages of growth, and a volume ratio of olivine to spinel of 100 to well over 1000. The olivine and spinel in this group have crystallized more slowly with little physical interaction, and show evidence that they have accumulated in a magma chamber. ?? 2006 Oxford University Press.

  18. Ringwoodite lamellae in olivine: Clues to olivine-ringwoodite phase transition mechanisms in shocked meteorites and subducting slabs.

    PubMed

    Chen, Ming; El Goresy, Ahmed; Gillet, Philippe

    2004-10-19

    The first natural occurrence of ringwoodite lamellae was found in the olivine grains inside and in areas adjacent to the shock veins of a chondritic meteorite, and these lamellae show distinct growth mechanism. Inside the veins where pressure and temperature were higher than elsewhere, ringwoodite lamellae formed parallel to the [101] planes of olivine, whereas outside they lie parallel to the (100) plane of olivine. The lamellae replaced the host olivine from a few percent to complete. Formation of these lamellae relates to a diffusion-controlled growth of ringwoodite along shear-induced planar defects in olivine. The planar defects and ringwoodite lamellae parallel to the [101] planes of olivine should have been produced in higher shear stress and temperature region than that parallel to the (100) plane of olivine. This study suggests that the time duration of high pressure and temperature for the growth of ringwoodite lamellae might have lasted at least for several seconds, and that an intracrystalline transformation mechanism of ringwoodite in olivine could favorably operate in the subducting lithospheric slabs in the deep Earth. PMID:15479764

  19. Relative strengths of orthopyroxene and olivine at asthenospheric conditions

    NASA Astrophysics Data System (ADS)

    Holyoke, C. W., III; Raterron, P.; Girard, J.

    2014-12-01

    Orthopyroxene is the second most common mineral in the Earth's upper mantle. However, very little is known about its strength relative to olivine and clinopyroxene, both of which are well studied. Analyses of microstructures in peridotites containing orthopyroxene and olivine that were deformed at lithospheric conditions (relatively low temperatures and pressures) indicate that the orthopyroxene is stronger than surrounding olivine. In contrast, analyses of microstructures in asthenospheric peridotite xenoliths indicate that olivine and orthopyroxene have similar strengths. In order to better determine the pressure, temperature and strain rate sensitivity of the strength of orthopyroxene aggregates, we have performed an experimental study on stacked cylinders of orthopyroxene aggregates and olivine aggregates in the D-DIA. Cylinders of Bamble orthopyroxene (d~5-30 microns) or San Carlos olivine (d~25 microns) were hot-pressed in-situ at 1300oC for 1 hour prior to deformation. Although the assemblies and powders were dried at >100oC for >12 hours prior to installation in the apparatus, minor concentrations of water were observed (OPx ~ 500 H/106 Si; Ol ~ 200 H/106 Si). Multiple deformation steps were performed in each experiment over a range of strain rates (5x10-6 to 2x10-4/s) at a single temperature and pressure (T = 1000 - 1400oC and P = 2 - 5 GPa). At almost all conditions tested in these experiments, the orthopyroxene aggregates deformed at the same strain rate as the olivine cylinders, indicating both materials have the same stress exponent and very similar activation enthalpy. The microstructures observed in both the orthopyroxene and olivine cylinders are consistent with dislocation creep and lattice preferred orientations consistent with those observed in naturally deformed peridotites. These results indicate that at asthenospheric mantle conditions, the strengths of orthopyroxene and olivine in the dislocation creep field are very similar.

  20. Deciphering magma histories through phosphorus zoning in olivine

    NASA Astrophysics Data System (ADS)

    Ersoy, Ö.; Nikogosian, I.; Mason, P. R. D.; van Bergen, M.

    2015-12-01

    Since olivine is usually the first major phase to crystallize from basaltic magma, its primary chemistry is a sensitive tracer of the early evolution of volcanic systems. However, fast diffusion and homogenization under magmatic conditions frequently modifies the original composition of olivine, which hampers the reconstruction of cooling histories and magma evolution from the chemistry and zoning patterns of phenocrysts in erupted products. Phosphorous is a notable exception due to its sluggish diffusion in olivine crystals and silicate melts, as igneous olivines almost always display complex zoning patterns. Phosphorus zoning in olivine has been linked either to crystallization rate variations and diffusion controlled growth or to strong compositional controls on melt-mineral partitioning. We illuminate the versatility of P-in-olivine with a comprehensive EPMA and LA-ICPMS dataset on olivines from Italian potassium rich mafic lavas and the primitive melt inclusions (MI) that they host. The olivines are characterized by P concentrations from limit of quantification (22 ppm) to 435 ppm P with MIs containing up to 2.2 wt.% P2O5. High resolution (1-2 μm per pixel) element maps show both fine oscillatory and large scale sector zoning in P, which is uncorrelated with zoning in any other element. The MIs are virtually always surrounded by P-depleted zones that are also depleted in Cr and enriched in Al and Ti, which we attribute to a combination of supply-limited slow growth and melt compositional controls on partitioning behavior imposed by the boundary layer. We demonstrate that P zoning carries valuable information on the nature and timing of magmatic events such as mingling/mixing, wall-rock assimilation and subsequent re-equilibration processes. P-in-olivine is most promising to distinguish multiple generations of MIs, as a guide to study their mode of entrapment and to disclose the origin of primary heterogeneities.

  1. Experimental Reproduction of Olivine rich Type-I Chondrules

    NASA Technical Reports Server (NTRS)

    Smith, Robert K.

    2005-01-01

    Ordinary chondritic meteorites are an abundant type of stony meteorite characterized by the presence of chondrules. Chondrules are small spheres consisting of silicate, metal, and sulfide minerals that experienced melting in the nebula before incorporation into chondritic meteorite parent bodies. Therefore, chondrules record a variety of processes that occurred in the early solar nebula. Two common types of unequilibrated chondrules with porphyritic textures include FeO-poor (type I) and FeO-rich (type II) each subdivided into an A (SiO2-poor) and B (SiO2-rich) series. Type IA chondrules include those with high proportions of olivine phenocrysts (>80% olivine) and type IB chondrules include those with high proportions of pyroxene phenocrysts (<20% olivine). An intermediate composition, type IAB chondrules include those chondrules in which the proportion of olivine phenocrysts is between 20-80%. We conducted high-temperature laboratory experiments (melting at 1550 C) to produce type I chondrules from average unequilibrated ordinary chondrite (UOC) material mixed with small amounts of additional olivine. The experiments were conducted by adding forsteritic rich olivine (San Carlos olivine, Fo 91) to UOC material (GRO 95544) in a 30/70 ratio, respectively. Results of these high temperature experiments suggest that we have replicated type IA chondrule textures and compositions with dynamic crystallization experiments in which a heterogeneous mixture of UOC (GRO 95544) and olivine (San Carlos olivine) were melted at 1550 C for 1 hr. and cooled at 5-1000 C/hr using graphite crucibles in evacuated silica tubes to provide a reducing environment.

  2. Materials Data on LiMnPO4 (SG:2) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-07-09

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  3. Materials Data on LiMnPO4 (SG:146) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-07-09

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  4. Materials Data on LiMnPO4F (SG:2) by Materials Project

    DOE Data Explorer

    Kristin Persson

    2016-02-05

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  5. Olivine and spinel fabric development in lineated peridotites

    NASA Astrophysics Data System (ADS)

    German, Lindsey; Newman, Julie; Chatzaras, Vasileios; Kruckenberg, Seth; Stewart, Eric; Tikoff, Basil

    2016-04-01

    Investigation of olivine and spinel fabrics in lineated harzburgites from the Red Hills peridotite massif, New Zealand, reveals that the spinel grain population records the same orientation of the principal finite strain axes as olivine grains, however, olivine grains generally record stronger fabric anisotropy. Further, olivine crystallographic preferred orientation (CPO) reflects the constrictional kinematic context of these rocks. In these harzburgites, deformed at ~1200 °C and >6 kbar, spinel grains are variably oriented and display weak to no CPO. Shape fabric in spinels, determined using X-ray computed tomography (XRCT) indicates a range of geometries (L>S, L=S and LOlivine grains (mean diameter: 0.13 - 0.27 mm) exhibit evidence for dislocation creep, including subgrains, undulose extinction and a strong shape preferred orientation, with long axes parallel or subparallel to the mean spinel long axis orientation derived from XRCT. Olivine fabric analyses, carried out using Image SXM on grain traces from optical photomicrographs of two mutually perpendicular thin sections from each sample, yield moderately to strongly prolate fabrics (L>S tectonites) for olivine in all samples. CPO, plotted with respect to lineation and foliation as defined by XRCT analyses of spinel grains, is characterized by [100] maxima parallel or subparallel to the lineation; [010] and [001] form girdles perpendicular to the lineation, consistent with the D-type CPO for olivine. Olivine CPO is typically interpreted in the context of deformation conditions (e.g., temperature, stress) based on experimental studies. However, the D-type CPO for olivine is generally associated with deformation at relatively lower temperatures than suggested by the mineral compositions in these rocks. Our data suggest that olivine CPO may not only respond to deformation conditions, but may be controlled by the

  6. The fate of olivine in the lower crust: Pseudomorphs after olivine in coronitic metagabbro from the Grenville Orogen, Ontario

    NASA Astrophysics Data System (ADS)

    Kendrick, J. L.; Jamieson, R. A.

    2016-09-01

    Orthopyroxene-oxide symplectites after olivine are among the most enigmatic features of corona assemblages in metagabbros. Two coronitic metagabbro bodies from the Algonquin suite in the Grenville Orogen, Ontario, contain exceptionally well preserved orthopyroxene + Fe-Ti oxide symplectite formed during prograde Ottawan (ca. 1060 Ma) granulite-facies metamorphism. Based on textural evidence, we propose a new hypothesis for the formation of these symplectites. Under oxidising conditions associated with fluid infiltration, magmatic olivine and ilmenite underwent a coupled reaction whereby magnetite produced by oxidation of olivine replaced adjacent igneous ilmenite. Ilmenite was re-precipitated as a fine-grained intergrowth with orthopyroxene and some magnetite in the former olivine sites. This hypothesis is supported by textural evidence showing partial replacement of magmatic ilmenite by magnetite and a close spatial association between magmatic oxides and orthopyroxene + Fe-Ti oxide symplectite, which locally radiates from ilmenite into olivine. Measured orthopyroxene/oxide ratios in the symplectite (20-35% oxides) agree with the ratio predicted from the proposed reaction (ca. 30%). Coronas and pseudomorphs formed during high-grade metamorphism, with increasing fO2 interpreted to result from fluid infiltration at near-peak conditions of ca. 13 kbar, 800 °C. The same samples contain red-brown fine-grained aggregates interpreted as iddingsite pseudomorphs after olivine. Raman spectroscopy suggests that the iddingsite consists largely of amorphous silica and Fe-hydroxide; textural evidence indicates that it formed by late-stage oxidation and hydration of olivine that survived earlier metamorphism. The unusual co-occurrence of granulite-facies pseudomorphs after olivine with an alteration product formed at near-surface conditions indicates that some olivine may survive protracted high-grade metamorphism in environments where fluid access is limited.

  7. Kamacite and olivine in ordinary chondrites - Intergroup and intragroup relationships

    NASA Astrophysics Data System (ADS)

    Rubin, A. E.

    1990-05-01

    Results are presented from high-precision electron microprobe analyses of olivine and kamacite in a suite of 134 ordinary chondrites (OCs). The compositional ranges of these phases are defined for each OC group (high total Fe, low total Fe, and low total Fe/low metallic Fe). Anomalous OCs that have olivine and/or kamacite compositions that lie outside the established ranges are identified. The phases in the chondritic clasts of the Netschaevo iron meteorite are characterized to determine the relationship between Netschaevo and OCs. Intragroup variations of olivine and kamacite compositions with petrologic type are examined and OCs that contain olivine and/or kamacite grains with aberrant compositions are identified as fragmental breccias. Also, a search for new metallic Fe-Ni phases with extreme compositions is conducted. As a result of these analyses, several meteorites are reclassified.

  8. Olivine Weathering: Abiotic Versus Biotic Processes as Possible Biosignatures

    NASA Technical Reports Server (NTRS)

    Longazo, T. G.; Wentworth, S. J.; McKay, D. S.; Southam, G.; Clemett, S. J.

    2001-01-01

    A preliminary study to determine how abiotic versus biotic processes affect the weathering of olivine crystals. Perhaps the differences between these weathering processes could be used as biosignatures. Additional information is contained in the original extended abstract.

  9. Thermo-Reflectance Spectra of Eros: Unambiguous Detection of Olivine

    NASA Technical Reports Server (NTRS)

    Lucey, P. G.; Hinrichs, J. L.; Urquhart-Kelly, M.; Wellnitz, D.; Bell, J. F., III; Clark, B. E.

    2001-01-01

    Olivine is readily detected on 433 Eros using the new thermo-reflectance spectral technique applied to near-IR spectra obtained at Eros by the NEAR spacecraft. Additional information is contained in the original extended abstract.

  10. Systematics of Vanadium in Olivine from Planetary Basalts

    NASA Technical Reports Server (NTRS)

    Karner, J. M.; Papike, J. J.; Shearer, C. K.

    2002-01-01

    The systematics of vanadium in olivines from the Earth, Moon and Mars allows for the comparison of planetary basalt origin and igneous setting and process. Additional information is contained in the original extended abstract.

  11. The Grand Tack, Vesta, and the Missing Olivine Problem

    NASA Astrophysics Data System (ADS)

    Consolmagno, G. J.; Rubie, D. C.; Golabek, G. J.

    2016-08-01

    The anisotropic expansion of coarse peridotites means that differentiated protoplanets may disrupt into large cohesive basaltic fragments but mm-sized olivine crystals susceptible to fractionation, possibly contributing to chondritic matrix material.

  12. Olivine and Pyroxene Compositions in Fine-Grained Chondritic Materials

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Frank, D.

    2011-01-01

    Our analyses of the Wild-2 samples returned by the Stardust Mission have illuminated critical gaps in our understanding of related astromaterials. There is a very large database of olivine and low-calcium pyroxene compositions for coarse-grained components of chondrites, but a sparse database for anhydrous silicate matrix phases. In an accompanying figure, we present comparisons of Wild-2 olivine with the available chondrite matrix olivine major element data. We thus have begun a long-term project measuring minor as well as major element compositions for chondrite matrix and chondritic IDPs, and Wild 2 grains. Finally, we wish to re-investigate the changes to fine-grained olivine and low-Ca pyroxene composition with progressive thermal metamorphism. We have examined the LL3-4 chondrites which because of the Hayabusa Mission have become very interesting.

  13. Aluminum speeds up the hydrothermal alteration of olivine

    NASA Astrophysics Data System (ADS)

    Andreani, Muriel; Daniel, Isabelle; Pollet-Villard, Marion

    2014-05-01

    The reactivity of ultramafic rocks toward hydrothermal fluids controls chemical fluxes at the interface between the internal and external reservoirs of silicate planets. On Earth, hydration of ultramafic rocks is ubiquitous and operates from deep subduction zones to shallow lithospheric environments where it considerably affects the physical and chemical properties of rocks and can interact with the biosphere. This process also has key emerging societal implications, such as the production of hydrogen as a source of carbon-free energy. To date, the chemical model systems used to reproduce olivine hydrothermal alteration lead to the formation of serpentine with sluggish reaction rates. Although aluminum is common in geological environments and in hydrothermal systems in particular, its role in serpentinization or olivine dissolution has not been investigated under hydrothermal conditions. Nevertheless, abundant Al supply is expected in fluids released from dehydration of metapelites in subduction zones as well as during the hydrothermal alteration of gabbros at mid-ocean ridges. Aluminum was also abundant in primitive environments of both the Earth and Mars, stored in either Al-rich minerals like plagioclase or Al-enriched ultramafic lavas. We have investigated the role of Al on the hydrothermal alteration of olivine in a series of experiments performed in a low-pressure diamond anvil cell while following the reaction progress in situ by optical imaging and Raman spectroscopy. Experiments were run for 4.5 to 7.5 days with two olivine grains reacted in saline water (0.5 molal NaCl) at 200°C and 300°C, and P=200 MPa. After two days, olivine crystals were fully transformed to an aluminous serpentine, also enriched in iron. The presence of Al in the hydrothermal fluid increases the rate of olivine serpentinization by more than one order of magnitude by enhancing olivine solubility and serpentine precipitation. The mechanism responsible for this increased solubility

  14. Space Weathering of Olivine: Samples, Experiments and Modeling

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Berger, E. L.; Christoffersen, R.

    2016-01-01

    Olivine is a major constituent of chondritic bodies and its response to space weathering processes likely dominates the optical properties of asteroid regoliths (e.g. S- and many C-type asteroids). Analyses of olivine in returned samples and laboratory experiments provide details and insights regarding the mechanisms and rates of space weathering. Analyses of olivine grains from lunar soils and asteroid Itokawa reveal that they display solar wind damaged rims that are typically not amorphized despite long surface exposure ages, which are inferred from solar flare track densities (up to 10 (sup 7 y)). The olivine damaged rim width rapidly approaches approximately 120 nm in approximately 10 (sup 6 y) and then reaches steady-state with longer exposure times. The damaged rims are nanocrystalline with high dislocation densities, but crystalline order exists up to the outermost exposed surface. Sparse nanophase Fe metal inclusions occur in the damaged rims and are believed to be produced during irradiation through preferential sputtering of oxygen from the rims. The observed space weathering effects in lunar and Itokawa olivine grains are difficult to reconcile with laboratory irradiation studies and our numerical models that indicate that olivine surfaces should readily blister and amorphize on relatively short time scales (less than 10 (sup 3 y)). These results suggest that it is not just the ion fluence alone, but other variable, the ion flux that controls the type and extent of irradiation damage that develops in olivine. This flux dependence argues for caution in extrapolating between high flux laboratory experiments and the natural case. Additional measurements, experiments, and modeling are required to resolve the discrepancies among the observations and calculations involving solar wind processing of olivine.

  15. Dissolution of olivine in basaltic liquids: experimental observations and applications.

    USGS Publications Warehouse

    Thornber, C.R.; Huebner, J.S.

    1985-01-01

    Rates of olivine dissolution in synthetic lunar basalt 77115 and a silica-enriched 77115 composition (Sil-77115) at superliquidus temperatures have been determined. Dissolution-rate data have been applied to the problem of the thermal history of fragment-laden impact-melt rocks of the lunar highlands. Textural and chemical criteria are discussed for the recognition of olivine resorption (and growth) phenomena in igneous rocks. -J.A.Z.

  16. Olivine Instability: An Experimental View of Mechanism of Deep Earthquakes

    NASA Astrophysics Data System (ADS)

    Long, H.; Weidner, D.; Li, L.; Chen, J.; Wang, L.

    2007-12-01

    Olivine (¦Á-(Mg,Fe)2SiO4) is the major constituent of the upper mantle and the ocean lithosphere. In subduction zone, where the earthquakes happen, the rheology of slab is mainly controlled by that of olivine. Several different mechanisms for deep focus earthquakes have been suggested, which include olivine instability (Bridgman, 1936; Orowan, 1960; Post, 1977; Ogawa, 1987; Hobbs and Ord, 1988; Kao and Chen, 1995), shear-induced melting (Griggs, 1954, 1972; Griggs and Handin, 1960; Griggs and Baker, 1969), phase transformation (Bridgman, 1945; Benioff, 1963; Meade and Jeanloz, 1989), dehydration of hydrous specimens (Meade and Jeanloz, 1991), and olivine metastability-induced anticrack (Green and Houston, 1995). Since the low temperature of the ¡°cold¡± slab, which can be as low as 600¡ãC in transition zone, olivine may still exist there and thus its shear instability may still be the possible mechanism for the deep-focus earthquakes. In our experimental study on deformation of San Carlos olivine at subduction zone conditions carried out on a D-DIA apparatus, Sam85 at X17B2, NSLS, we observed that the transitional temperature between regimes of insensitive to temperature and sensitive to temperature can be as high as 900¡ãC or even higher for the annealed polycrystal olivine sample, while that for unannealed sample can be as low as 450¡ãC. Our results for the unannealed sample are consistent to the result of Raterron et al (2004), which is concluded from the relaxation experiments. The annealed and unannealed olivine can be present the natural olivine in non-fault systems and that in pre-existing fault systems in subduction zone, respectively. We therefore propose a new olivine instability model with a ¡°sandwich¡± formation for the deep focus earthquakes: In this model the pre-existing fault system is surrounded by the no-fault systems. When the slab dives down, the olivine in both systems undergoes a stress- build-up process and can hold very high

  17. Minor elements in relict olivine grains of deep-sea spheres: Match with Mg-rich olivines from C2 meteorites

    NASA Technical Reports Server (NTRS)

    Smith, J. V.; Steele, I. M.; Brownlee, D. E.

    1984-01-01

    The bulk composition and relict minerals of meteoroid ablation spheres from deep sea sediments can be related to the parental material, and bulk compositions and elemental ratios favor a CI/CM affinity for most spheres. Although largely melted, some deep sea spheres (DSS) have retained rare grains apparently unmodified chemically by ablation heating or seawater alteration. Minor elements in relict olivines for comparison with compositions of olivines in known meteorites were analyzed. All relict olivines are very Mg rich. No terrestrial olivines match the chemical features which reinforces other evidence for an extraterrestrial origin. There is no match with achondritic olivines. Mg rich olivines occur in all types of carbonaceous meteorites, but the minor elements of most DSS olivines do not match with those for Allende (C3) olivines, and fit poorly with those of Murchison (C2) olivines. There is a good fit for Fe and Cr with those of the olivines in the unusual Belgica 7904 (C2) meteorite (3). It seems likely that the relict olivines of at least many deep sea spheres are chemically related to olivines in at least one C2 meteorite.

  18. Extraction of in situ cosmogenic 14C from olivine

    USGS Publications Warehouse

    Pigati, J.S.; Lifton, N.A.; Timothy, Jull A.J.; Quade, Jay

    2010-01-01

    Chemical pretreatment and extraction techniques have been developed previously to extract in situ cosmogenic radiocarbon (in situ 14C) from quartz and carbonate. These minerals can be found in most environments on Earth, but are usually absent from mafic terrains. To fill this gap, we conducted numerous experiments aimed at extracting in situ 14C from olivine ((Fe,Mg)2SiO4). We were able to extract a stable and reproducible in situ 14C component from olivine using stepped heating and a lithium metaborate (LiBO2) flux, following treatment with dilute HNO3 over a variety of experimental conditions. However, measured concentrations for samples from the Tabernacle Hill basalt flow (17.3 ?? 0.3 ka4) in central Utah and the McCarty's basalt flow (3.0 ?? 0.2 ka) in western New Mexico were significantly lower than expected based on exposure of olivine in our samples to cosmic rays at each site. The source of the discrepancy is not clear. We speculate that in situ 14C atoms may not have been released from Mg-rich crystal lattices (the olivine composition at both sites was ~Fo65Fa35). Alternatively, a portion of the 14C atoms released from the olivine grains may have become trapped in synthetic spinel-like minerals that were created in the olivine-flux mixture during the extraction process, or were simply retained in the mixture itself. Regardless, the magnitude of the discrepancy appears to be inversely proportional to the Fe/(Fe+Mg) ratio of the olivine separates. If we apply a simple correction factor based on the chemical composition of the separates, then corrected in situ 14C concentrations are similar to theoretical values at both sites. At this time, we do not know if this agreement is fortuitous or real. Future research should include measurement of in situ 14C concentrations in olivine from known-age basalt flows with different chemical compositions (i.e. more Fe-rich) to determine if this correction is robust for all olivine-bearing rocks. ?? 2010 by the Arizona

  19. Olivine Composite Cathode Materials for Improved Lithium Ion Battery Performance

    SciTech Connect

    Ward, R.M.; Vaughey, J.T.

    2006-01-01

    Composite cathode materials in lithium ion batteries have become the subject of a great amount of research recently as cost and safety issues related to LiCoO2 and other layered structures have been discovered. Alternatives to these layered materials include materials with the spinel and olivine structures, but these present different problems, e.g. spinels have low capacities and cycle poorly at elevated temperatures, and olivines exhibit extremely low intrinsic conductivity. Previous work has shown that composite structures containing spinel and layered materials have shown improved electrochemical properties. These types of composite structures have been studied in order to evaluate their performance and safety characteristics necessary for use in lithium ion batteries in portable electronic devices, particularly hybrid-electric vehicles. In this study, we extended that work to layered-olivine and spinel-olivine composites. These materials were synthesized from precursor salts using three methods: direct reaction, ball-milling, and a coreshell synthesis method. X-ray diffraction spectra and electrochemical cycling data show that the core-shell method was the most successful in forming the desired products. The electrochemical performance of the cells containing the composite cathodes varied dramatically, but the low overpotential and reasonable capacities of the spinel-olivine composites make them a promising class for the next generation of lithium ion battery cathodes.

  20. Tracing Oxygen Fugacity in Asteroids and Meteorites Through Olivine Composition

    NASA Technical Reports Server (NTRS)

    Sunshine, J. M.; Bus, S. J.; Burbine, T. H.; McCoy, T. J.

    2005-01-01

    Olivine absorptions are known to dominate telescopic spectra of several asteroids. Among the meteorite collection, three groups (excluding Martian meteorites), the pallasites, brachinites, and R group chondrites are plausible analogs to olivine-rich asteroids in that they are dominated by olivine. These meteorite groups have distinct petrologic origins. The primitive achondrite brachinites (which include both depleted and undeleted subgroups) are products of relatively minor differentiation and evolved in oxidizing environments. R chondrites are also thought to have formed in high oxygen states, but are closely related to ordinary chondrites (yet with their own distinct compositions and oxygen isotopic signatures). In contrast, pallasites, widely thought to be mantle components from much more evolved bodies, formed in more reducing environments. Petrologic indicators that are identifiable in spectral data must be used in order to infer the petrologic history of asteroids from surveys of their actual population. As discussed below, olivine composition (e.g. Fa#) can provide key constraints in exploring the origin and significance of olivine dominated asteroids.

  1. Weathering of olivine under CO2 atmosphere: A martian perspective

    NASA Astrophysics Data System (ADS)

    Dehouck, E.; Gaudin, A.; Mangold, N.; Lajaunie, L.; Dauzères, A.; Grauby, O.; Le Menn, E.

    2014-06-01

    Recent analyses from the Curiosity rover at Yellowknife Bay (Gale crater, Mars) show sedimentary rocks deposited in a lacustrine environment and containing smectite clays thought to derive from the alteration of olivine. However, little is known about the weathering processes of olivine under early martian conditions, and about the stability of smectite clays in particular. Here, we present a 3-month experiment investigating the weathering of forsteritic olivine powders (Fo90) under a dense CO2 atmosphere, and under present-day terrestrial conditions for comparison. The experiment also evaluates the potential effects of hydrogen peroxide (H2O2), as a representation of the highly oxidizing compounds produced by photochemical reactions throughout martian history. The weathered samples were characterized by means of near-infrared spectroscopy (NIR), X-ray diffraction (XRD), transmission electron microscopy with energy dispersive X-ray spectrometry (TEM-EDX), Mössbauer spectroscopy and thermogravimetry. The results show that a Mg-rich smectite phase formed from the weathering of olivine under CO2 conditions, although in lower abundance than under terrestrial conditions. The main secondary phase formed under CO2 turns out to be a silica-rich phase (possibly acting as a “passivating” layer) with a non-diagnostic near-infrared spectral signature. The use of H2O2 highlights the critical importance of both the redox conditions and Fe content of the initial olivine on the nature of the secondary phases.

  2. Textural evolution of polyhedral olivine experiencing rapid cooling rates

    NASA Astrophysics Data System (ADS)

    Faure, François; Schiano, Pierre; Trolliard, Gilles; Nicollet, Christian; Soulestin, Bernard

    2007-04-01

    Dynamic crystallization experiments in the CaO MgO Al2O3 SiO2 (CMAS) system have been used to investigate the change in crystal shape when pre-existing polyhedral olivine crystals are cooled rapidly (1,639 2,182°C/h). Polyhedral olivines are crystallized initially in a first step using a slow cooling rate (2°C/h), then skeletal and dendritic overgrowths develop on the polyhedral crystals during a subsequent fast cooling event. During this second episode small dendritic olivines also nucleate within the liquid phase. Observation of the experimental sample by optical microscopy shows that the polyhedral olivine shape progressively changes to a skeletal and then to a dendritic morphology in the following sequence: polyhedral ⇒ hopper polyhedral ⇒ dendritic polyhedral. This evolutional sequence is discussed in terms of changes in the crystal growth conditions during cooling and a general relation between these olivine dynamic crystallization experiments and the integrated model of crystal growth by Sunagawa (Bull Minér 104:81 87, 1981, Morphology of crystals, Terra Scientific Publishing Company, 1987) is proposed.

  3. An olivine-free mantle source of Hawaiian shield basalts.

    PubMed

    Sobolev, Alexander V; Hofmann, Albrecht W; Sobolev, Stephan V; Nikogosian, Igor K

    2005-03-31

    More than 50 per cent of the Earth's upper mantle consists of olivine and it is generally thought that mantle-derived melts are generated in equilibrium with this mineral. Here, however, we show that the unusually high nickel and silicon contents of most parental Hawaiian magmas are inconsistent with a deep olivine-bearing source, because this mineral together with pyroxene buffers both nickel and silicon at lower levels. This can be resolved if the olivine of the mantle peridotite is consumed by reaction with melts derived from recycled oceanic crust, to form a secondary pyroxenitic source. Our modelling shows that more than half of Hawaiian magmas formed during the past 1 Myr came from this source. In addition, we estimate that the proportion of recycled (oceanic) crust varies from 30 per cent near the plume centre to insignificant levels at the plume edge. These results are also consistent with volcano volumes, magma volume flux and seismological observations. PMID:15800614

  4. Reversibility of Lpo in Olivine during Deformation at High Pressure

    NASA Astrophysics Data System (ADS)

    Li, L.; Weidner, D. J.

    2014-12-01

    Olivine texture has been reported as an important contributor to the seismic anisotropy in the upper mantle. Experimental studies of deformation of olivine have also shown flow-driven lattice preferred orientation. In this study, we focus on in situ control and monitoring of LPO formation of olivine using synchrotron X-ray radiation coupled with DDIA multi-anvil deformation device. Using an energy-dispersive X-ray coupled a 10-element SSD detector; we apply a sinusoidal stress on the sample, which allows identification of growth of LPO in the specimen with relative robust signal even with small strain fields. Our data show palpable correlations among stress, strain and LPO as well as the variations among sub-grains marked by individual (hkl). This study is to demonstrate the versatile functions of X-ray for characterizing the deformation study of minerals.

  5. Exogenic olivine on Vesta from Dawn Framing Camera color data

    NASA Astrophysics Data System (ADS)

    Nathues, Andreas; Hoffmann, Martin; Schäfer, Michael; Thangjam, Guneshwar; Le Corre, Lucille; Reddy, Vishnu; Christensen, Ulrich; Mengel, Kurt; Sierks, Holger; Vincent, Jean-Baptist; Cloutis, Edward A.; Russell, Christopher T.; Schäfer, Tanja; Gutierrez-Marques, Pablo; Hall, Ian; Ripken, Joachim; Büttner, Irene

    2015-09-01

    In this paper we present the results of a global survey of olivine-rich lithologies on (4) Vesta. We investigated Dawn Framing Camera (FC) High Altitude Mapping Orbit (HAMO) color cubes (∼60 m/pixel resolution) by using a method described in Thangjam et al. (Thangjam, G., Nathues, A., Mengel, K., Hoffmann, M., Schäfer, M., Reddy, V., Cloutis, E.A., Christensen, U., Sierks, H., Le Corre, L., Vincent, J.-B, Russell, C.T. [2014b]. Meteorit. Planet. Sci. arXiv:1408.4687 [astro-ph.EP]). In total we identified 15 impact craters exhibiting olivine-rich (>40 wt.% ol) outcrops on their inner walls, some showing olivine-rich material also in their ejecta and floors. Olivine-rich sites are concentrated in the Bellicia, Arruntia and Pomponia region on Vesta's northern hemisphere. From our multi-color and stratigraphic analysis, we conclude that most, if not all, of the olivine-rich material identified is of exogenic origin, i.e. remnants of A- or/and S-type projectiles. The olivine-rich lithologies in the north are possibly ejecta of the ∼90 km diameter Albana crater. We cannot draw a final conclusion on their relative stratigraphic succession, but it seems that the dark material (Nathues, A., Hoffmann, M., Cloutis, E.A., Schäfer, M., Reddy, V., Christensen, U., Sierks, H., Thangjam, G.S., Le Corre, L., Mengel, K., Vincent, J.-B., Russell, C.T., Prettyman, T., Schmedemann, N., Kneissl, T., Raymond, C., Gutierrez-Marques, P., Hall, I. Büttner, I. [2014b]. Icarus (239, 222--237)) and the olivine-rich lithologies are of a similar age. The origin of some potential olivine-rich sites in the Rheasilvia basin and at crater Portia are ambiguous, i.e. these are either of endogenic or exogenic origin. However, the small number and size of these sites led us to conclude that olivine-rich mantle material, containing more than 40 wt.% of olivine, is basically absent on the present surface of Vesta. In combination with recent impact models of Veneneia and Rheasilvia (Clenet, H

  6. Applicability of Henry's Law to helium solubility in olivine

    NASA Astrophysics Data System (ADS)

    Jackson, C.; Parman, S. W.; Kelley, S. P.; Cooper, R. F.

    2013-12-01

    Applicability of Henry's Law to helium solubility in olivine We have experimentally determined helium solubility in San Carlos olivine across a range of helium partial pressures (PHe) with the goal of quantifying how noble gases behave during partial melting of peridotite. Helium solubility in olivine correlates linearly with PHe between 55 and 1680 bar. This linear relationship suggests Henry's Law is applicable to helium dissolution into olivine up to 1680 bar PHe, providing a basis for extrapolation of solubility relationships determined at high PHe to natural systems. This is the first demonstration of Henry's Law for helium dissolution into olivine. Averaging all the data of the PHe series yields a Henry's coefficient of 3.8(×3.1)×10-12 mol g-1 bar-1. However, the population of Henry's coefficients shows a positive skew (skewness = 1.17), i.e. the data are skewed to higher values. This skew is reflected in the large standard deviation of the population of Henry's coefficients. Averaging the median values from each experiment yields a lower Henry's coefficient and standard deviation: 3.2(× 2.3)×10-12 mol g-1 bar-1. Combining the presently determined helium Henry's coefficient for olivine with previous determinations of helium Henry's coefficients for basaltic melts (e.g. 1) yields a partition coefficient of ~10-4. This value is similar to previous determinations obtained at higher PHe (2). The applicability of Henry's Law here suggests helium is incorporated onto relatively abundant sites within olivine that are not saturated by 1680 bar PHe or ~5×10-9 mol g-1. Large radius vacancies, i.e. oxygen vacancies, are energetically favorable sites for noble gas dissolution (3). However, oxygen vacancies are not abundant enough in San Carlos olivine to account for this solubility (e.g. 4), suggesting the 3x10-12 mol g-1 bar-1 Henry's coefficient is associated with interstitial dissolution of helium. Helium was dissolved into olivine using an externally heated

  7. Iddingzitized olivine in mantle xenoliths: evidence for (really) early alteration

    NASA Astrophysics Data System (ADS)

    Low, P. C.; Schultz, L.; Stier, N.

    2011-12-01

    Iddingsite is an alteration product of olivine (or pyroxene) that contains goethite and some combination of maghemite, hematite, orthopyroxene, Mg-rich phyllosilicates, amorphous silica, and a temperature and a pressure-appropriate SiO2 polymorph and lacks the definite structure or chemical composition requisite of classification as a mineral. The process of iddingsitization is most commonly discussed as a low-temperature, near-surface phenomenon involving the oxidation and inorganic hydroxylation of olivine during weathering. High-temperature iddingsite (sometimes referred to as magmatic iddingsite) is also discussed in the literature and is generally attributed to reactions that occur at low pressure in response unusually high water content and/or high oxygen fugacity in pre-eruptive mafic magmas or during the process of extrusion and cooling or to hydrothermal metasomatism. Xenoliths from the Ponderosa flow of the Uinkaret Volcanic Field located along the Colorado River just downstream from Lava Falls in the Western Grand Canyon include spinel-bearing dunite, harzburgite, and olivine-rich lherzolite samples that exhibit geochemical characteristics that are consistent with residues of 5-17% partial melting. Olivine from xenoliths collected from this flow contain olivine that is either entirely fresh (no evidence of alteration) or olivine that has been ubiquitously partially iddingzitized with some samples containing both the green-colored fresh samples and the red-colored altered samples mere centimeters apart. Preliminary in situ FTIR mapping of water peaks in the region of 3700-3000 cm-1 indicate notable peak near 3680 cm-1 (a region of the spectrum associated with the presences of serpentine minerals) in altered samples. Iddingsite exhibits two distinct morphologies in these samples, one thicker (about 1 micrometer across) occurring mostly along fractures in the olivine grains, and the other much thinner occurring along crystallographically-oriented planes in

  8. An olivine-free mantle source of Hawaiian shield basalts.

    PubMed

    Sobolev, Alexander V; Hofmann, Albrecht W; Sobolev, Stephan V; Nikogosian, Igor K

    2005-03-31

    More than 50 per cent of the Earth's upper mantle consists of olivine and it is generally thought that mantle-derived melts are generated in equilibrium with this mineral. Here, however, we show that the unusually high nickel and silicon contents of most parental Hawaiian magmas are inconsistent with a deep olivine-bearing source, because this mineral together with pyroxene buffers both nickel and silicon at lower levels. This can be resolved if the olivine of the mantle peridotite is consumed by reaction with melts derived from recycled oceanic crust, to form a secondary pyroxenitic source. Our modelling shows that more than half of Hawaiian magmas formed during the past 1 Myr came from this source. In addition, we estimate that the proportion of recycled (oceanic) crust varies from 30 per cent near the plume centre to insignificant levels at the plume edge. These results are also consistent with volcano volumes, magma volume flux and seismological observations.

  9. Barred olivine 'chondrules' in lunar spinel troctolite 62295

    NASA Technical Reports Server (NTRS)

    Roedder, E.; Weiblen, P. W.

    1977-01-01

    Several objects have been found in sections of lunar igneous spinel troctolite 62295 that resemble certain meteoritic barred olivine chondrules. Each consists of an apparently spherical single crystal of Fo90 olivine, approximately 0.6-0.8 mm in diameter, containing a set of approximately 30-40 subparallel stringers of An95 plagioclase, whereas the stringers in ordinary meteoritic chondrules consist of glass. The olivine of the 62295 chondrules is also more magnesian, and is radially zoned, having a relatively iron-rich core and rim and an iron-poor intermediate zone. Several possible origins are proposed: impact-generated melt globules solidified in flight, spherical phenocrysts, and meteoritic chondrules, but none of these seems adequate to explain the detailed observations.

  10. Effect of water, stress, and pressure on the lattice-preferred orientation (LPO) of olivine and various examples of the LPOs of olivine recently found in nature

    NASA Astrophysics Data System (ADS)

    Jung, Haemyeong

    2010-05-01

    Seismic anisotropy in the upper mantle is often considered to be caused by lattice-preferred orientation (LPO) of olivine. Experimental studies on the deformation of olivine at high pressure and high temperature showed that water, stress, and temperature affect the development of LPO of olivine (Jung & Karato, 2001; Katayama et al., 2004; Jung et al., 2006; Katayama & Karato, 2006). Recent experimental study of harzburgite at high pressure and high temperature under low stress and dry conditions revealed that pressure also affects the development of LPO of olivine (Jung et al., 2009). I will review experimental studies on the deformation of olivine at high pressure and high temperature. And then, I will present various types of olivine LPOs found recently in natural rocks such as type-B, -C, -D and -E which are considered to be caused by water, stress, and pressure. Seismic anisotropy from the LPOs of olivine will be also discussed.

  11. The Identity of Hydrous Defects Controlling the Rheology of Olivine

    NASA Astrophysics Data System (ADS)

    Faul, U.; David, E. C.; Cline, C. J., II; Berry, A.; Jackson, I.

    2015-12-01

    The reduction of the creep strength of minerals due to the presence of water is well established. The nature of the relevant hydrous defect(s) is perhaps less well understood. Standard treatments examine intrinsic defects of a pure crystal, but impurity-related defects are not usually considered. Natural olivine contains monovalent (Na) and trivalent (e.g. Al) trace elements in concentrations that exceed the concentration of intrinsic defects by up to an order of magnitude. They therefore are potentially important as agents for water-weakening. Hydrated defects - both intrinsic and impurity-related - systematically affect infrared absorption spectra, which can therefore be used for their identification and quantification. Experiments with olivine in contact with a range of buffer assemblages (e.g. MgO and enstatite) have shown that the infrared spectra of natural olivine can only be reproduced experimentally in the presence of titanium. Doping with a range of trivalent cations shows systematics in the infrared spectra related to the ionic radius of the dopants, confirming that the spectra are sensitive to the bonding environment and can be used to identify particular defects. To investigate the relationship between hydrous, titanium-related defects and creep strength we conducted deformation experiments on synthetic Fo90 olivine that was buffered by enstatite and doped with titanium. The infrared spectra of the deformed samples show absorption bands at the same wave numbers and relative intensity as natural olivine, indicating that the experimental samples contain the same hydrous defects. Fitting the creep data from samples with a range of water contents determined from these absorption bands shows a near linear relationship between strain rate and water content, consistent with published observations. The experiments therefore show that the rheology of hydrous olivine is determined by hydrated impurity-related defects rather than intrinsic point defects.

  12. Primary magmas at Oldoinyo Lengai: The role of olivine melilitites

    NASA Astrophysics Data System (ADS)

    Keller, Jörg; Zaitsev, Anatoly N.; Wiedenmann, Daniel

    2006-10-01

    The paper describes olivine melilitites at Oldoinyo Lengai, Tanzania, and from tuff cones from the Tanzanian rift valley in the vicinity of Oldoinyo Lengai. Oldoinyo Lengai is the only active carbonatite volcano and is distinguished by its alkali-rich natrocarbonatites. Lengai is also unique for its extreme peralkaline silicate lavas related directly to the natrocarbonatites. Primitive olivine melilitites are, according to their Mg# and Ni, Cr contents, the only candidates in the Lengai area for primary melt compositions. Incompatible trace elements, including REE, constrain the melting process in their sub-lithospheric sources to very low degrees of partial melting in the garnet stability field. The strong peralkaline trend at Oldoinyo Lengai is already recognisable in these primary or near-primary melts. More evolved olivine melilitites, with Mg# < 60 allow the fractionation line in its major and trace element expressions to be followed. Nevertheless, a large compositional gap separates the olivine melilitites and olivine-poorer melilitites from the phonolites and nephelinites that form the bulk of the Lengai cone. These silicate lavas show a high degree of peralkalinity and are highly evolved with very low Mg, Ni and Cr. Prominent examples of the recent evolution are the combeite-wollastonite nephelinites that are unique for Lengai. In their Sr, Nd, and Pb isotope relationships the olivine melilitites define a distinct group with the most depleted Sr and Nd ratios and the most radiogenic Pb isotopes. They are closest to a supposed HIMU end member of the Lengai evolution, which is characterised by an extreme spread in isotopic ratios, explained as a mixing line between HIMU and EM1-like mantle components.

  13. Amoeboid olivine aggregates from CH carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Krot, Alexander N.; Park, Changkun; Nagashima, Kazuhide

    2014-08-01

    Amoeboid olivine aggregates (AOAs) in CH carbonaceous chondrites are texturally and mineralogically similar to those in other carbonaceous chondrite groups. They show no evidence for alteration and thermal metamorphism in an asteroidal setting and consist of nearly pure forsterite (Fa<3; in wt%, CaO = 0.1-0.8, Cr2O3 = 0.04-0.48; MnO < 0.5), anorthite, Al-diopside (in wt%, Al2O3 = 0.7-8.1; TiO2 < 1), Fe,Ni-metal, spinel, and, occasionally, low-Ca pyroxene (Fs1Wo2-3), and calcium-aluminum-rich inclusions (CAIs). The CAIs inside AOAs are composed of hibonite, grossite, melilite (Åk13-44), spinel, perovskite, Al,Ti-diopside (in wt%, Al2O3 up to 19.6; TiO2 up to 13.9), and anorthite. The CH AOAs, including CAIs within AOAs, have isotopically uniform 16O-rich compositions (average Δ17O = -23.4 ± 2.3‰, 2SD) and on a three-isotope oxygen diagram plot along ∼slope-1 line. The only exception is a low-Ca pyroxene-bearing AOA 1-103 that shows a range of Δ17O values, from -24‰ to -13‰. Melilite, grossite, and hibonite in four CAIs within AOAs show no evidence for radiogenic 26Mg excess (δ26Mg). In contrast, anorthite in five out of six AOAs measured has δ26Mg corresponding to the inferred initial 26Al/27Al ratio of (4.3 ± 0.7) × 10-5, (4.2 ± 0.6) × 10-5, (4.0 ± 0.3) × 10-5, (1.7 ± 0.2) × 10-5, and (3.0 ± 2.6) × 10-6. Anorthite in another AOA shows no resolvable δ26Mg excess; an upper limit on the initial 26Al/27Al ratio is 5 × 10-6. We infer that CH AOAs formed by gas-solid condensation and aggregation of the solar nebula condensates (forsterite and Fe,Ni-metal) mixed with the previously formed CAIs. Subsequently they experienced thermal annealing and possibly melting to a small degree in a 16O-rich gaseous reservoir during a brief epoch of CAI formation. The low-Ca pyroxene-bearing AOA 1-103 may have experienced incomplete melting and isotope exchange in an 16O-poor gaseous reservoir. The lack of resolvable δ26Mg excess in melilite, grossite, and

  14. Grain Boundary Structurally-Bonded Water in Olivine Aggregates

    NASA Astrophysics Data System (ADS)

    Wang, L.

    2008-12-01

    Water storage capacity of nominally anhydrous olivine has been extensively investigated because of its numerous geophysical and geochemical implications for the Earth's dynamic mantle. However, all previous experimental research has been concentrated on the water solubility in single crystals of olivine. Grain boundary as potential storage sites for water in the mantle has not been experimentally studied, in part because solubility experiments were always performed under water-saturated condition, rendering the examination of grain boundaries nearly impossible due to the presence of free water. In the present study we have conducted annealing experiments on forsterite at 5 - 6 GPa and 1200 °C and at water- undersaturated condition. Duration was typically 2 - 3 hours. A small amount of enstatite or periclase was added to the starting forsterite powder (including a few large olivine grains) to buffer the silica activity, while oxygen fugacity was controlled by using various capsule materials (Re, Fe, or BN). FTIR analyses were performed on both single crystal and polycrystalline olivine in doubly-polished thin section of each experimental charge. The results are as follows: (1) single crystal and polycrystalline olivine in the same charge always yielded similar IR pattern, indicating all absorption peaks are due to similar structurally-bonded water (i.e., hydroxyl); (2) water content of periclase-buffered (i.e., low silica activity) sample is at least one order of magnitude higher than those of enstatite-buffered and unbuffered (pure forsterite) samples; (3) under reducing environment (Fe or BN capsule), water content of polycrystalline olivine is always higher than that of single crystal by at lease a factor of 5, regardless of silica activity buffering. We therefore infer that large amount of structurally-bonded water is stored at grain boundaries; (4) with decreasing oxygen fugacity, IR spectra of olivine are increasingly dominated by an absorption peak centered

  15. Grinding methods to enhance the reactivity of olivine

    SciTech Connect

    Summers, Cathy A.; Dahlin, David C.; Rush, Gilbert E.; O'Connor, William K.; Gerdemann, Stephen J.

    2004-01-01

    The Albany Research Center (ARC) conducted studies of mechanical activation by conventional and ultra-fine grinding techniques to enhance olivine reactivity in mineral carbonation reactions. Activated olivine is one of several solid feed materials used at ARC in reactions with carbon dioxide to form carbonate minerals. This paper compares grinding techniques via energy demand data and product characteristics, including particle size distributions, surface areas, full width at half maximum (FWHM) XRD analyses, and particle morphology by SEM analyses. Reactivity was gauged by percent conversion to carbonate in subsequent carbonation tests.

  16. The complex relationship between olivine abundance and thermal inertia on Mars

    NASA Astrophysics Data System (ADS)

    Hanna, Romy D.; Hamilton, Victoria E.; Putzig, Nathaniel E.

    2016-07-01

    We examine four olivine-bearing regions at a variety of spatial scales with thermal infrared, visible to near-infrared, and visible imagery data to investigate the hypothesis that the relationship between olivine abundance and thermal inertia (i.e., effective particle size) can be used to infer the occurrence of olivine chemical alteration during sediment production on Mars. As in previous work, Nili Fossae and Isidis Planitia show a positive correlation between thermal inertia and olivine abundance in Thermal Emission Spectrometer (TES) and Thermal Emission Imaging System (THEMIS) data, which could be interpreted as indicating olivine chemical weathering. However, geomorphological analysis reveals that relatively olivine-poor sediments are not derived from adjacent olivine-rich materials, and therefore, chemical weathering cannot be inferred based on the olivine-thermal inertia relationship alone. We identify two areas (Terra Cimmeria and Argyre Planitia) with significant olivine abundance and thermal inertias consistent with sand, but no adjacent rocky (parent) units having even greater olivine abundances. More broadly, global analysis with TES reveals that the most typical olivine abundance on Mars is ~5-7% and that olivine-bearing (5-25%) materials have a wide range of thermal inertias, commonly 25-600 J m-2 K-1 s-1/2. TES also indicates that the majority of olivine-rich (>25%) materials have apparent thermal inertias less than 400 J m-2 K-1 s-1/2. In summary, we find that the relationship between thermal inertia and olivine abundance alone cannot be used in infer olivine weathering in the examined areas, that olivine-bearing materials have a large range of thermal intertias, and therefore that a complex relationship between olivine abundance and thermal inertia exists on Mars.

  17. Chemical zonation in olivine-hosted melt inclusions

    NASA Astrophysics Data System (ADS)

    Newcombe, M. E.; Fabbrizio, A.; Zhang, Youxue; Ma, C.; Le Voyer, M.; Guan, Y.; Eiler, J. M.; Saal, A. E.; Stolper, E. M.

    2014-07-01

    Significant zonation in major, minor, trace, and volatile elements has been documented in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (e.g., MgO, FeO, Cr2O3, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H2O, and F, components with a lower concentration in the host olivine than in the melt (e.g., Al2O3, SiO2, Na2O, K2O, TiO2, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions, concurrent with diffusive propagation of the boundary layer toward the inclusion center. Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na2O, K2O) by coupling to slow diffusing components such as SiO2 and Al2O3. Concentrations of H2O and F decrease toward the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects. A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150-13,000 °C h-1 from the liquidus down to ~1,000 °C, consistent with previously determined cooling rates for

  18. Influence of aluminum on the hydrothermal alteration rate of olivine

    NASA Astrophysics Data System (ADS)

    Andreani, M.; Daniel, I.; Pollet-Villard, M.

    2013-12-01

    The reactivity of ultramafic rocks under hydrothermal conditions controls chemical fluxes at the interface between the internal and external reservoirs of silicate planets. On Earth, hydration of ultramafic rocks is ubiquitous and operates from deep subduction zones to shallow lithospheric environments where it considerably affects the physical and chemical properties of rocks and can interact with the biosphere. This process also has key emerging societal implications, such as the production of hydrogen as a source of carbon-free energy. To date, the chemical model systems used to reproduce olivine hydrothermal alteration lead to the formation of serpentine with sluggish reaction rates. Although aluminum is common in geological environments and in hydrothermal systems in particular, its role in serpentinization or olivine dissolution has not been investigated under hydrothermal conditions. Nevertheless, abundant Al supply is expected in fluids released from dehydration of metapelites in subduction zones as well as during the hydrothermal alteration of gabbros at mid-ocean ridges. Aluminum was also abundant in primitive environments of both the Earth and Mars, stored in either Al-rich minerals like plagioclase or Al-enriched ultramafic lavas. We have investigated the role of Al on the hydrothermal alteration of olivine in a series of experiments performed in a low-pressure diamond anvil cell while following the reaction progress in situ by optical imaging and by confocal Raman spectroscopy. Experiments were run for 4.5 to 7.5 days with two olivine grains reacted in saline water (0.5 molal NaCl) at 200°C and 300°C, and P=200 MPa. After two days, olivine crystals were fully transformed to an aluminous serpentine, also enriched in iron. The very fast precipitation of serpentine may inhibit magnetite nucleation here. However, this does not rule out an H2 production since serpentines classically incorporate non negligible amount of ferric iron in their structure. The

  19. Formation of P-Rich Olivine in DaG 978 Carbonaceous Chondrite Through Fluid-Assisted Metamorphism

    NASA Astrophysics Data System (ADS)

    Zhang, A. C.; Li, Y.; Chen, J. N.; Gu, L. X.; Wang, R. C.

    2016-08-01

    We describe an occurrence of P-rich olivine in the DaG 978 carbonaceous chondrite. Different from other natural P-rich olivine, the P-rich olivine should have formed through fluid-assisted metamorphism.

  20. Solar Radiation Management and Olivine Dissolution Methods in Climate Engineering

    NASA Astrophysics Data System (ADS)

    Kone, S.

    2014-12-01

    An overview of solar radiation management and olivine dissolution methods allows to discuss, comparatively, the benefits and consequences of these two geoengineering techniques. The combination of those two techniques allows to concomitantly act on the two main agents intervening in global warming: solar radiation and carbon dioxide. The earth surface temperature increases due mainly to carbon dioxide (a greenhouse gas) that keeps the solar radiation and causes the global warming. Two complementary methods to mitigate climate change are overviewed: SRM method, which uses injected aerosols, aims to reduce the amount of the inbound solar radiation in atmosphere; and olivine dissolution in water, a key chemical reaction envisaged in climate engineering , aiming to reduce the amount of the carbon dioxide in extracting it from atmosphere. The SRM method works on scenarios of solar radiation decrease and the olivine dissolution method works as a carbon dioxide sequestration method. Olivine dissolution in water impacts negatively on the pH of rivers but positively in counteracting ocean acidification and in transporting the silica in ocean, which has benefits for diatom shell formation.

  1. Textural evidence bearing on the origin of isolated olivine crystals in C2 carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Richardson, S. M.; Mcsween, H. Y., Jr.

    1978-01-01

    In some cases the mechanical competence of chondrules in carbonaceous chondrites has been reduced by alteration of their mesostasis glass to friable phyllosilicate, providing a mechanism by which euhedral olivines can be separated from chondrules. Morphological features of isolate olivine grains found in carbonaceous chondrites are similar to those of olivine phenocrysts in chondrules. These observations suggest that the isolated olivine grains formed in chondrules, by crystallization from a liquid, rather than by condensation from a vapor.

  2. Synthesis and characterization of LiCo1/3Mn1/3Fe1/3PO4/C nanocomposite cathode of lithium batteries with high rate performance

    NASA Astrophysics Data System (ADS)

    Akimoto, Sou; Taniguchi, Izumi

    2013-11-01

    Olivine structured LiCo1/3Mn1/3Fe1/3PO4/C nanocomposites were prepared by a combination of spray pyrolysis at 300 °C and wet ball-milling followed by heat treatment at 500 °C for 4 h in a 3%H2 + N2 atmosphere. The formation of a solid solution between LiCoPO4, LiMnPO4, and LiFePO4 at this composition was confirmed by X-ray diffraction analysis. Scanning electron microscopy and transmission electron microscopy with equipped energy dispersive spectroscopy verified that the LiCo1/3Mn1/3Fe1/3PO4/C nanocomposites were agglomerates of LiCo1/3Mn1/3Fe1/3PO4 primary particles with a geometric mean diameter of 107 nm and a uniform chemical composition, and carbon was well distributed on the surface of the agglomerates. The LiCo1/3Mn1/3Fe1/3PO4/C nanocomposite cathode exhibited a high discharge capacity of 159 mAh g-1 at 0.05 C in the potential range of 2.0-5.0 V, corresponding to 94% of theoretical capacity. The capacity retention was 87% after 50 cycles at a charge-discharge rate of 1 C. Furthermore, the rate capability test showed that the high capacity still was retained even at 5 C and 20 C rate with 106 and 72 mAh g-1, respectively.

  3. Geoengineering potential of artificially enhanced silicate weathering of olivine.

    PubMed

    Köhler, Peter; Hartmann, Jens; Wolf-Gladrow, Dieter A

    2010-11-23

    Geoengineering is a proposed action to manipulate Earth's climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate the potential of a specific geoengineering technique, carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification, because it influences the global climate via the carbon cycle. If important details of the marine chemistry are taken into consideration, a new mass ratio of CO(2) sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. In our calculations for the Amazon and Congo river catchments, a maximum annual dissolution of 1.8 and 0.4 Pg of olivine seems possible, corresponding to the sequestration of 0.5 and 0.1 Pg of C per year, but these upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2. Open water dissolution of fine-grained olivine and an enhancement of the biological pump by the rising riverine input of silicic acid might increase our estimate of the carbon sequestration, but additional research is needed here. We finally calculate with a carbon cycle model the consequences of sequestration rates of 1-5 Pg of C per year for the 21st century by this technique.

  4. Diffusive over-hydration of olivine-hosted melt inclusions

    NASA Astrophysics Data System (ADS)

    Hartley, Margaret E.; Neave, David A.; Maclennan, John; Edmonds, Marie; Thordarson, Thor

    2015-09-01

    The pre-eruptive water content of magma is often estimated using crystal-hosted melt inclusions. However, olivine-hosted melt inclusions are prone to post-entrapment modification by H+ diffusion as they re-equilibrate with their external environment. This effect is well established for the case of H+ loss from olivine-hosted inclusions that have cooled slowly in degassed magma. Here we present evidence for the opposite effect: the addition of H+ into inclusions that are held in melts that are enriched in H2O with respect to the trapped melts. The compositional variability in a suite of 211 olivine-hosted inclusions from the Laki and Skuggafjöll eruptions in Iceland's Eastern Volcanic Zone indicates that diffusive H+ gain governs the H2O content of incompatible trace element depleted inclusions. Individual eruptive units contain olivine-hosted inclusions with widely varying incompatible element concentrations but near-constant H2O. Furthermore, over 40% of the inclusions have H2 O /Ce > 380, significantly higher than the H2O/Ce expected in primary Icelandic melts or mid-ocean ridge basalts (150-280). The fact that the highest H2O/Ce ratios are found in the most incompatible element depleted inclusions indicates that hydration is a consequence of the concurrent mixing and crystallisation of compositionally diverse primary melts. Hydration occurs when olivines containing depleted inclusions with low H2O contents are juxtaposed against more hydrous melts during mixing. Melt inclusions from a single eruption may preserve evidence of both diffusive H+ loss and H+ gain. Trace element data are therefore vital for determining H2O contents of melt inclusions at the time of inclusion trapping and, ultimately, the H2O content of the mantle source regions.

  5. Geoengineering potential of artificially enhanced silicate weathering of olivine.

    PubMed

    Köhler, Peter; Hartmann, Jens; Wolf-Gladrow, Dieter A

    2010-11-23

    Geoengineering is a proposed action to manipulate Earth's climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate the potential of a specific geoengineering technique, carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification, because it influences the global climate via the carbon cycle. If important details of the marine chemistry are taken into consideration, a new mass ratio of CO(2) sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. In our calculations for the Amazon and Congo river catchments, a maximum annual dissolution of 1.8 and 0.4 Pg of olivine seems possible, corresponding to the sequestration of 0.5 and 0.1 Pg of C per year, but these upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2. Open water dissolution of fine-grained olivine and an enhancement of the biological pump by the rising riverine input of silicic acid might increase our estimate of the carbon sequestration, but additional research is needed here. We finally calculate with a carbon cycle model the consequences of sequestration rates of 1-5 Pg of C per year for the 21st century by this technique. PMID:21059941

  6. Geoengineering potential of artificially enhanced silicate weathering of olivine

    PubMed Central

    Köhler, Peter; Hartmann, Jens; Wolf-Gladrow, Dieter A.

    2010-01-01

    Geoengineering is a proposed action to manipulate Earth’s climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate the potential of a specific geoengineering technique, carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification, because it influences the global climate via the carbon cycle. If important details of the marine chemistry are taken into consideration, a new mass ratio of CO2 sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. In our calculations for the Amazon and Congo river catchments, a maximum annual dissolution of 1.8 and 0.4 Pg of olivine seems possible, corresponding to the sequestration of 0.5 and 0.1 Pg of C per year, but these upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2. Open water dissolution of fine-grained olivine and an enhancement of the biological pump by the rising riverine input of silicic acid might increase our estimate of the carbon sequestration, but additional research is needed here. We finally calculate with a carbon cycle model the consequences of sequestration rates of 1–5 Pg of C per year for the 21st century by this technique. PMID:21059941

  7. Evidence for equilibrium conditions during the partitioning of nickel between olivine and komatiite liquids.

    USGS Publications Warehouse

    Budahn, J.R.

    1986-01-01

    Olivine-liquid partition coefficients for Ni(DNi), calculated from Ni vs MgO abundance variations in komatiite series basalts, compare favourably with experimentally determined values, if Ni variations in olivine-controlled basalts can be modelled with an equation that assumes equilibrium between the entire olivine crystal and its coexisting liquid.-J.A.Z.

  8. Experimental Deformation of Olivine Single Crystal at Mantle P and T: Pressure Effect on Olivine Dislocation Slip-System Activities

    NASA Astrophysics Data System (ADS)

    Paul, R.; Girard, J.; Chen, J.; Amiguet, E.

    2008-12-01

    Seismic velocity anisotropies observed in the upper mantle are interpreted from lattice preferred orientations (LPO) produced experimentally in olivine, which depends on the dominant dislocation slip systems. At low pressure P<3 GPa, mantle temperature (T) and in dry conditions, olivine [100] dislocation slip dominates the less active [001] slip. This tends to align crystal fast velocity [100] axis with the principal shear direction. Yet recent high-pressure deformation experiments (Couvy et al., 2004, EJM, 16, 877; Raterron et al., 2007, Am. Min., 92, 1436; Raterron et al., 2008, Phys. Earth Planet. Int., doi:10.1016/j.pepi.2008.07.026) show that [001](010) slip system dominates [100](010) system in the (P,T) range of the deep upper mantle. This may promote a shear-parallel slow-velocity [001] axis and may explain the seismic-velocity attenuation observed at depth >200 km (Mainprice et al., 2005, Nature, 433, 731). In order to further constrain the effect of P on olivine slip system activities, which is classically quantified by the activation volume V* in power creep laws, deformation experiments were carried out in poor water condition, at P>5 GPa and T=1400°C, on pure forsterite (Fo100) and San Carlos olivine crystals, using the Deformation-DIA apparatus at the X17B2 beamline of the NSLS (Upton, NY). Ten crystals were oriented in order to active either [100] slip alone or [001] slip alone in (010) plane, or both [100](001) and [001](100) systems together. Constant applied stress σ <300 MPa and specimen strain rates were monitored in situ using time-resolved x-ray diffraction and radiography, respectively, for a total of 27 investigated steady state conditions. The obtained rheological data were compared with data previously obtained in comparable T and σ conditions, but at room P, by Darot and Gueguen (1981, JGR, 86, 6219) for Fo100 and by Bai et al. (1991, JGR, 96, 2441) for San Carlos olivine. This new set of data confirms previous deformation data

  9. Performance improvement of lithium manganese phosphate by controllable morphology tailoring with acid-engaged nano engineering.

    PubMed

    Guo, Hui; Wu, Chunyang; Liao, Longhuan; Xie, Jian; Zhang, Shichao; Zhu, Peiyi; Cao, Gaoshao; Zhao, Xinbing

    2015-01-20

    Olivine-type lithium manganese phosphate (LiMnPO4) has been considered as a promising cathode for next-generation Li-ion batteries. Preparation of high-performance LiMnPO4 still remains a great challenge because of its intrinsically low Li-ion/electronic conductivity. In this work, significant performance enhancement of LiMnPO4 has been realized by a controllable acid-engaged morphology tailoring from large spindles into small plates. We find that acidity plays a critical role in altering the morphology of the LiMnPO4 crystals. We also find that size decrease and plate-like morphology are beneficial for the performance improvement of LiMnPO4. Among the plate-like samples, the one with the smallest size shows the best electrochemical performance. After carbon coating, it can deliver high discharge capacities of 104.0 mAh g(-1) at 10 C and 85.0 mAh g(-1) at 20 C. After 200 cycles at 1 C, it can still maintain a high discharge capacity of 106.4 mAh g(-1), showing attractive applications in high-power and high-energy Li-ion batteries.

  10. Lattice preferred orientations of olivine in the schistosed antigorite serpentinite

    NASA Astrophysics Data System (ADS)

    Soda, Y.; Ando, J.; Mizukami, T.; Morishita, T.

    2011-12-01

    The lattice preferred orientation (LPO) of the schistosed antigorite serpentinite is considered as causes of the seismic anisotropy observed at the subduction zones (Katayama et al., 2009; Jung, 2011) and the natural examples are reported by several researchers (Bezacier et al., 2010; Hirauchi et al., 2010; Soda and Takagi, 2010). Formation process of the antigorite LPO is unclear, especially at primary serpentinized stage. To understand the development of micro-structures of antigorite serpentinite, we made structural analyses of serpentinite schist and the former peridotite fabric. Samples were taken from lenticular serpentinite bodies (< 1km) stack in Jurassic accretionary complex, Toba area, Southwest Japan. The serpentinite consist of olivine, antigorite, meta-clinopyroxene and Cr-spinel. The foliation and lineation of serpentinite is defined by parallel alignment of elongated olivine grain and antigorite blades, which make up mylonitic textures, such as a porphyroclast system and composite planar fabric. Antigorite blades show syn-kinematic growth in pressure shadows and pull-apart of olivine porphyroclast. In the less serpentinized part, antigorite blades are crystallized along the grain boundary of olivine. We measure the LPOs of coarse olivine grains in the serpentinite schist using a u-stage. The X, Y and Z directions represent directions of lineation, normal to lineation within the foliation and normal to foliation, respectively. The LPOs of olivine show point maximum or partial girdle distribution, and these concentrated crystal axes are incongruous with X, Y and Z direction. The a[100] axes of olivine are parallel to the serpentinite foliation, and form a point maximum several degrees away from the Y direction. The b[010] axes and the c[001] axes are concentrated Z and X direction forming a partial girdle normal to Y direction, respectively. Boudier et al. (2010) have reported the topotactic relationship between olivine and antigorite. They show that

  11. High-temperature elasticity of iron-bearing olivines

    NASA Astrophysics Data System (ADS)

    Isaak, Donald G.

    1992-02-01

    The first high-temperature data on the nine adiabatic elastic moduli for iron-bearing olivine are reported. These measurements are on two single-crystal specimens of natural olivine at ambient pressure and from room temperature to a maximum of 1500 K. The two specimens contain 8 and 9 modal percent fayalite, which required the oxygen fugacity be controlled at high temperature to preserve their chemical stability. The rectangular parallelepiped resonance apparatus was adapted to buffer the specimens from the atmosphere with a mixture of CO and CO2 gas. A small increase (˜1-2 GPa) in the adiabatic bulk modulus of each specimen, over that of end-member forsterite, was found. The data are high quality to extreme temperatures, with good agreement found when comparing the temperature derivatives of the elastic moduli of the two specimens. Neither specimen exhibits measurable nonlinear temperature dependence in the computed isotropic bulk and shear moduli, which is in contrast to published forsterite data. The temperature derivatives of the isotropic bulk modulus KS are (-1.69, -1.80) × 10-2 GPa K-1 for the two olivine specimens, and the shear modulus G derivatives are (-1.38, -1.36) × 10-2 GPa K-1. These derivatives are only slightly larger in magnitude than |(∂KS/∂T)P| = 1.56 × 10-2 and |(∂G/∂T)P| = 1.30 × 10-2 GPa K-1 found previously for iron-bearing olivine over a very small temperature range. There are also no significant differences between the temperature derivatives found here and the average derivatives of end-member forsterite from data retrieved over a slightly larger temperature range. Several dimensionless parameters have been calculated from these results and are discussed in view of systematics which bear on high-pressure phases in Earth's transition zone. One result from these systematics related to the seismic velocities in the Earth, and especially the shear wave velocities, is that an olivine content of less than 50% is implied at the 400

  12. Real Time Pore Structure Evolution during Olivine Mineral Carbonation

    NASA Astrophysics Data System (ADS)

    Zhu, W.; Fusseis, F.; Lisabeth, H. P.; Xiao, X.

    2014-12-01

    Aqueous carbonation of ultramafic rocks has been proposed as a promising method for long-term, secure sequestration of carbon dioxide. While chemical kinetics data indicate that carbonation reaction in olivine is one of the fastest among the mg-bearing minerals, in practice, the factors that limit the extent and rate of carbonation in ultramafic rocks are fluid supply and flux. On the one hand, reaction products could produce passivating layer that prohibits further reactions. On the other hand, the increases in solid volume during carbonation could lead to cracking and create new fluid paths. Whether carbonation in ultramafic rocks is self-limiting or self-sustaining has been hotly debated. Experimental evidence of precipitation of reaction products during olivine carbonation was reported. To date, reaction-driven cracking has not been observed. In this paper, we present the first real-time pore structure evolution data using the x-ray synchrotron microtomography. Sodium bicarbonate (NaHCO3) solution was injected into porous olivine aggregates and in-situ pore structure change during olivine carbonation at a constant confining pressure (12 MPa) and a temperature of 200oC was captured at 30 min. interval for ~160 hours. Shortly after the experiment started, filling-in of the existing pores by precipitation of reaction products was visible. The size of the in-fills kept increasing as reactions continued. After ~48 hours, cracking around the in-fill materials became visible. After ~60 hours, these cracks started to show a clear polygonal pattern, similar to the crack patterns usually seen on the surface of drying mud. After ~72 hours, some of the cracks coalesced into large fractures that cut-through the olivine aggregates. New fractures continued to develop and at the end of the experiment, the sample was completely disintegrated by these fractures. We also conducted nanotomography experiments on a sub-volume of the reacted olivine aggregate. Orthogonal sets of

  13. Olivine vitrophyres - A nonpristine high-Mg component in lunar breccia 14321

    NASA Technical Reports Server (NTRS)

    Shervais, John W.; Taylor, Lawrence A.; Lindstrom, Marilyn M.

    1988-01-01

    The presence of olivine vitrophyres in breccia 14321 is discussed, suggesting that olivine vitrophyres could account for the high-Mg component of soils and breccias in the lunar highlands. The olivine vitrophyre clasts from 14321 have high bulk MgO and the Mg/(Mg+Fe) ratio is 78 percent. The olivine vitrophyres are impact melt rocks and are rich in KREEP. The high MgO concentration is manifest by skeletal quench crystals of olivine that constitute about 30 percent of the mode.

  14. Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars

    NASA Technical Reports Server (NTRS)

    Treiman, A. H.

    2005-01-01

    Carbonate globules in ALH84001 are associated with small olivine grains an unexpected finding because the olivines equilibrated at high T while the carbonate is chemically zoned and unequilibrated. A possible explanation comes from a terrestrial analog on Spitsbergen (Norway), where some carbonate globules grew in cavities left by aqueous dissolution of olivine. For ALH84001, the same process may have acted, with larger olivines dissolved out and smaller ones shielded inside orthopyroxene. Carbonate would have been deposited in holes where the olivine had been. Later shocks crushed remaining void space, and mobilized feldspathic glass around the carbonates.

  15. Chemical variation and zoning of olivine in lunar dunite 72415 - Near-surface accumulation

    NASA Technical Reports Server (NTRS)

    Ryder, Graham

    1992-01-01

    Electron microprobe remeasurements have been used to reevaluate the range of olivine compositions, including CaO, in lunar dunite sample 72415 and compare that range with olivines in established plutonic rocks. Olivines from ferroan anorthosite 62237 and samples from the Stillwater intrusion were analyzed; literature data for other lunar and terrestrial plutonic samples were used for comparisons. The analyses show that the lunar dunite 72415 contains a range of olivine compositions, that the olivines are zoned, and that they have CaO abundances that are consistent with shallow hypabyssal rather than deep plutonic accumulation.

  16. Experimental constraints on magnetic stability of chondrules and the paleomagnetic significance of dusty olivines

    NASA Astrophysics Data System (ADS)

    Uehara, Minoru; Nakamura, Norihiro

    2006-10-01

    Dynamic crystallization experiments are conducted under a magnetic field to determine both magnetic and mineralogical properties of chondrules. The experiment reproduced synthetic dusty olivine samples that were formed by a high temperature reduction of an initially fayalitic olivine. Backscattered-electron microscopy observations confirmed that synthetic dusty olivine contains abundant fine, submicron-sized Ni-poor Fe inclusions in the cores of MgO-rich olivine grains, similar to that in natural chondrules. Alternating field demagnetization experiments of dusty olivine samples indicate mean destructive fields of up to 80 mT, suggesting the submicron-sized Fe inclusions are a carrier of stable remanence. In natural chondrules, fine Fe inclusions in the dusty olivine may have been armored against chemical alteration by surrounding host olivine crystals. Since the fine Fe inclusions were probably heated above the Curie temperature during the last chondrule forming events, the fine Fe inclusions in dusty olivine can acquire thermal remanent magnetization during the chondrule formation event. Theoretical time-temperature relation of such fine-grained Fe (kamacite) grains suggested that a paleomagnetic data observed above 490 °C in thermal demagnetization experiments of dusty olivines is reliable despite the low-grade metamorphism of unequilibrated ordinary chondrites (e.g., LL3.0). Therefore, the presence of fine Fe inclusions in dusty olivine in unequilibrated ordinary chondrites constrains that such dusty olivine in chondrules is a good candidate as an un-altered and stable magnetic recorder of the early solar magnetic field.

  17. Waveform effects of a metastable olivine tongue in subducting slabs

    NASA Technical Reports Server (NTRS)

    Vidale, John E.; Williams, Quentin; Houston, Heidi

    1991-01-01

    Velocity models of subducting slabs with a kinetically-depressed olivine to beta- and gamma-spinel transition are constructed, and the effect that such structures would have on teleseismic P waveforms are examined using a full-wave finite-difference method. These 2D calculations yielded waveforms at a range of distances in the downdip direction. The slab models included a wedge-shaped, low-velocity metastable olivine tongue (MOTO) to a depth of 670 km, as well as a plausible thermal anomaly; one model further included a 10-km-thick fast layer on the surface of the slab. The principal effect of MOTO is to produce grazing reflections at wide angles off the phase boundary, generating a secondary arrival 0 to 4 seconds after the initial arrival depending on the take-off angle. The amplitude and timing of this feature vary with the lateral location of the seismic source within the slab cross-section.

  18. The solubility of olivine in basaltic liquids - An ionic model

    NASA Technical Reports Server (NTRS)

    Herzberg, C. T.

    1979-01-01

    A model is presented which enables the temperature at which olivine is in equilibrium with any alkali-depleted basaltic compound to be calculated to within + or - 30 C. It is noted that the error increases substantially when applied to terrestrial basalts which contain several weight percent alkalis. In addition the model predicts and quantifies the reduced activity of SiO4(4-) monomers due to increasing SiO2 concentrations in the melt. It is shown that the coordination of alumina in melts which precipitate olivine only appears to be dominantly octahedral, while titanium acts as a polmerizing agent by interconnecting previously isolated SiO4(4-) monomers. It is concluded that the model is sufficiently sensitive to show that there are small repulsive forces between Mg(2+) and calcium ions which are in association with normative diopside in the melt.

  19. Grinding methods to enhance the reactivity of olivine

    SciTech Connect

    Summers, Cathy A.; Dahlin, David C.; Rush, Gilbert E.; O'Connor, William K.; Gerdemann, Stephen J.

    2005-08-01

    The Albany Research Center (ARC) conducted studies of mechanical activation by conventional and ultrafine grinding techniques to enhance olivine reactivity in mineral carbonation reactions. Activated olivine is one of several solid feed materials used at ARC in reactions with carbon dioxide to form carbonate minerals. This paper compares grinding techniques via energy demand data and product characteristics, including particle size distributions, surface areas, full-width-at-half-maximum (FWHM) XRD analyses, and particle morphology by SEM analyses. Reactivity was calculated by percent conversion to carbonate in subsequent carbonation tests. Particle size reduction has the greatest impact on reactivity, and wet grinding is more energy efficient than dry grinding. Large additional inputs of energy to increase surface area or reduce crystallinity do not result in proportional improvements in reactivity.

  20. Experimental evidence of reaction-induced fracturing during olivine carbonation

    NASA Astrophysics Data System (ADS)

    Zhu, Wenlu; Fusseis, Florian; Lisabeth, Harrison; Xing, Tiange; Xiao, Xianghui; De Andrade, Vincent; Karato, Shun-ichiro

    2016-09-01

    Mineral carbonation, a process that binds CO2 in the form of carbonates by silicate weathering, is widespread on the Earth's surface. Because of the abundance of silicate rocks and the permanence of the carbonated solids, sequestering CO2 via mineral carbonation has generated lots of interests. However, it is unclear how the fluid-rock reaction proceeds to completion in spite of an increasing solid volume. We conducted a mineral carbonation experiment in which a sintered olivine aggregate reacted with a sodium bicarbonate solution at reservoir conditions. Time-resolved synchrotron X-ray microtomographic images show cracks in polygonal patterns arising in the surface layers and propagating into the interior of the olivine aggregate. The nanotomography data reveal that the incipient cracks intersect at right angles. We infer that stretching due to nonuniform volume expansion generates polygonal cracking of the surfaces. Our data shed new lights on the processes that control hydration and carbonation of peridotite.

  1. Chemical frost weathering of olivine: Experimental study and implications

    NASA Technical Reports Server (NTRS)

    Harris, S. L.; Huguenin, R. L.

    1987-01-01

    New experimental results are reported on the frost weathering of olivine. After first weathering, a decrease in Fe sup 2(+)M(2) absorption bands were noted. This decrease is related to the protonation of O(+) in the mineral. It is contented that this reaction may result in the regolith storage of 100 to 1000 m of H(sub 2) over the history of Mars.

  2. Olivine-rich asteroids in the main asteroid belt

    NASA Astrophysics Data System (ADS)

    DeMeo, Francesca E.; Polishook, David; Carry, Benoit; Moskovitz, Nick; Burt, Brian; Binzel, Rick

    2015-11-01

    Olivine-dominated asteroids, classified as A-types with near-infrared spectral measurements are largely thought to be the mantle remnants of disrupted differentiated small bodies. These A-type asteroids hold clues to asteroid differentiation and to the collisional history of those differentiated bodies. Preliminary studies of the abundance and distribution of A-type asteroids were performed by Carvano et al. (2010) and DeMeo & Carry (2013, 2014) using the Sloan Digital Sky Survey (SDSS). To confidently identify these olivine-dominated A-type asteroids, however, near-infrared spectral measurements are needed to identify the distinct broad and deep 1-micron olivine absorption feature. Using the Sloan Digital Sky Survey Moving Object Catalog to select A-type asteroid candidates, we have performed a near-infrared spectral survey of over 70 asteroids with SpeX on the IRTF. We present the abundance and distribution of A-type asteroids throughout the main asteroid belt and compare these results with similar surveys for basalt-rich V-type asteroids (e.g. Moskovitz et al. 2008). This work is supported by NASA under grant number NNX12AL26G issued through the Planetary Astronomy Program.

  3. Experimental Replication of Relict "Dusty" Olivine in Type 1B Chondrules

    NASA Technical Reports Server (NTRS)

    Lofgren, Gary E.; Le, L.

    2002-01-01

    Introduction: Relict "dusty" olivine is considered to be a remnants of previous chondrule forming events based on petrographic and chemical evidence. Dynamic crystallization experiments confirm that dusty olivine can be produced by reduction of FeO-rich olivine in Unequilibrated Ordinary Chondrite (UOC) material. The results of these experiments compliment those of who also produced dusty olivine, but from synthetic starting materials. Techniques: Dynamic crystallization experiments were conducted in which UOC material was reduced in presence of graphite. Starting material was coarsely ground GR095554 or WSG95300 that contained olivine of Fo 65-98. Approximately 75 mg. of UOC material was placed in a graphite crucible and sealed in an evacuated silica tube. The tube was suspended in a gas-mixing furnace operated at 1 log unit below the IW buffer. The experiments were as brief as 1.5 hrs up to 121 hrs. Results: Dusty olivine was produced readily in experiments melted at 1400 C for I hr. and cooled between 5 and 100 C/hr or melted at 1300-1400 C for 24 hours. Fe-rich olivine (dusty olivine precursors) that have been partially reduced were common in the experiments melted at 1400 C and cooled at 1000 C/hr or melted at 1200 C for 24 hrs. Relict olivine is absent in experiments melted at 1400 for 24 hrs, melted above 1400 C, or cooled more slowly than 10 C/hr. Relict olivine in the experiments has minimum Fo value of 83 . Thus even in the shortest experiments the most Fe-rich olivine has been altered significantly. The precursor olivine disappears in a few to many hours depending on temperature. The experiments show Fe-rich olivine in all stages of transition to the new dusty form. The olivine is reduced to form dusty olivine in a matter of a few hours at temperatures less than 1400 C and in minutes at higher temperatures. The reduction appears to proceed from the rim of the crystal inward with time. The reduction appears initially rectilinear as if controlled by

  4. Optimization of Carbon Coatings on LiFePO4

    SciTech Connect

    Doeff, Marca M.; Wilcox, James D.; Kostecki, Robert; Lau, Grace

    2005-07-14

    The electrochemical performance of LiFePO{sub 4} in lithium cells is strongly dependent on the structure (disordered/graphene or D/G ratio) of the in situ carbon produced during synthesis from carbon-containing precursors. Addition of pyromellitic acid (PA) prior to final calcination results in lower D/G ratios, yielding a higher-rate material. Further, improvements in electrochemical performance are realized when graphitization catalysts such as ferrocene are also added during LiFePO{sub 4} preparation, although overall carbon content is still less than 2 wt.%.

  5. Comparison of LiFePO4 from different sources

    SciTech Connect

    Striebel, Kathryn; Shim, Joongpyo; Srinivasan, Venkat; Newman, John

    2004-06-21

    The lithium iron phosphate chemistry is plagued by the poor conductivity and slow diffusion in the solid phase. In order to alleviate these problems, various research groups have adopted different strategies including decreasing the particle sizes, increasing the carbon content, and adding dopants. In this study, we obtained LiFePO{sub 4} powders and/or electrodes from six different sources and used a combined model-experimental approach to compare the performance. Samples ranged from 0.4% to 15% ''in-situ'' carbon. In addition, particle sizes varied by as much as an order of magnitude between samples. The study detailed in this manuscript allows us to provide insight into the relative importance of the conductivity of the samples compared to the particle size, the impact of having a distribution in particle sizes, and ideas for making materials in order to maximize the power capability of this chemistry.

  6. Ringwoodite growth rates from olivine with ~75 ppmw H2O: Metastable olivine must be nearly anhydrous to exist in the mantle transition zone

    SciTech Connect

    Du Frane, Wyatt L.; Sharp, Thomas G.; Mosenfelder, Jed L.; Leinenweber, Kurt

    2013-04-15

    It has been previously demonstrated that as little as 300 ppmw H2O increases wadsleyite and ringwoodite growth rates to magnitudes that are inconsistent with the metastable olivine hypothesis. To further test this hypothesis, we present new ringwoodite growth rate measurements from olivine with ~75 ppmw H2O at 18 GPa and 700, 900, and 1100 °C. These growth rates are nearly identical to those from olivine with ~300 ppmw H2O, and significantly higher than those from nominally anhydrous olivine. We infer that transformation of olivine with 75-300 ppmw H2O is primarily enhanced by hydrolytic weakening of reaction rims, which reduces the elastic strain-energy barrier to growth. We present a new method for fitting nonlinear nominally anhydrous data, to demonstrate that reduction of growth rates by elastic strain energy is an additional requirement for metastable olivine. In conclusion, based on previous thermokinetic modeling, these enhanced growth rates are inconsistent with the persistence of metastable olivine wedges into the mantle transition zone. Metastable persistence of olivine into the mantle transition-zone would therefore require < 75 ppmw H2O.

  7. The origin of olivine-rich troctolites/plagioclase-dunites

    NASA Astrophysics Data System (ADS)

    Garapic, G.; Faul, U.; Kruckenberg, S. C.; Wiejaczka, J.; Newton, J. C.

    2015-12-01

    Olivine-rich troctolites or plagioclase dunites are a type of rock commonly found in oceanic crust and peridotite massifs that does not fit into a IUGS classification. Part of the reason is that their origin is poorly constrained, in particular whether these rocks are cumulates or residual mantle rocks. To avoid implications for origin or process Blackman et al. 2006 defined as olivine-rich troctolites rocks that contain > 70% olivine,with plagioclase, cpx and spinel. We examined this type of rock in Krivaja peridotite massif in Bosnia-Herzegovina where it occurs as massive outcrops with an area of several tens of square kilometres. The plagioclase dunites are underlain by peridotites that contain plagioclase patches indicative of melt migration. These peridotites are progressively depleted of pyroxene and cross-cut by gabbro veins. The plagioclase dunites have Mg# predominantly from 89 - 90 and Ni contents from 2500 - 3500 ppm, similar to the peridotites. EBSD mapping of whole thin sections shows orientation distribution functions (odf) that are unlike any of the fabric types observed in naturally or experimentally deformed rocks with a strong maximum in (001) near the foliation plane (although this plane is poorly defined) and weak girdles of the other two axes perpendicular to it. For comparison, we also mapped known cumulates from the Rum and Stillwater layered intrusions with somewhat lower Mg# of 84 - 86. The odf of these samples show a strong maximum of (010) perpendicular to the foliation plane and weak girdles of the other two axes in the plane. This fabric type has been explained by crystal settling and compaction in a magma chamber. Together these observations show that the plagioclase dunites from Krivaja, as well as rocks with similar characteristics e.g. from the Mid-Atlantic Ridge (Drouin et al. 2010) and Italy (Renna and Tribuzio, 2011) are not cumulates but are of mantle origin. An important characteristic of the plagioclase dunites is that the

  8. Fe/Mn in olivine of carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Steele, Ian M.

    1993-01-01

    Olivines in primitive meteorites show a range of Fe/Mn both within one grain and among grains suggesting that they have recorded changing conditions during or after growth. Because olivine should be an early forming phase, Fe/Mn is used here to infer these earliest conditions. Initial Fe/Mn in cores of isolated, euhedral forsterite in both C2 and C3 meteorites ranges from 25 to 35 but differs at grain edge. Murchison (C2) forsterites show Fe/Mn approaching 1.0 at the grain edge while Ornans Fe/Mn is near 60 at grain edge. These values are lower than the matrix Fe/Mn for both meteorites and the distinct difference in zoning profile indicates different processes operating during and after grain growth. The Fe/Mn of bulk samples from a particular source such as the Moon is nearly constant. Individual samples show variation suggesting that there is some fractionation of Mn from Fe. Minerals have their individual ranges of Fe/Mn which has been used to recognize different types of olivine within one meteorite. Extreme values of Fe/Mn below 1.0 occur in forsterite from some IDP's, UOC matrix, and C1 meteorites. There are apparently no detailed studies of Fe/Mn variation within single olivine grains. Forsterite grains in C2 and C3 carbonaceous chondrites show complex zoning, and the nearly pure forsterites (Fo greater than approximately 99.5) have high levels of some minor elements including Ti, Al, V, and Sc. There is disagreement on the original source of these grains and both chondrule and vapor growth have been proposed. In addition, there is clear evidence that diffusion has affected the outer margins but in some cases the whole grain. Within the cores, the FeO range is limited, and if growing under constant conditions, the Fe/Mn should be near constant as there is little fractionation of Mn from Fe by forsterite. Additionally, there are apparently no co-crystallizing phases as evidenced by a lack of common inclusions in the forsterites. These observations are now

  9. Low Temperature Plasticity of Olivine Determined by Nano-indentation

    NASA Astrophysics Data System (ADS)

    Skemer, P. A.; Kranjc, K.; Rouse, Z.; Flores, K.

    2015-12-01

    Earth's upper mantle is thought to deform mainly by dislocation creep, during which strain-rate and stress are related by a simple power law equation. However at much higher stresses there is a break-down in the power law relationship and strain-rate depends exponentially on stress. This phenomenon, known as low temperature plasticity, may be important in the shallow ductile or semi-brittle regions of the lithosphere, at the tips of cracks, or during high-stress laboratory experiments. Several studies have attempted to constrain the low-temperature rheology of olivine using micro-indentation or high pressure experiments. In this study we provide the first measurements of olivine rheology at low temperature using instrumented nano-indention. Although nano-indentation has been widely used in the materials sciences, its application in the Earth sciences has been very limited. Nano-indentation methods provide rheological measurements that are significantly more precise than other mechanical tests at high pressure and temperature. Moreover, experiments are rapid and largely non-destructive, so many tests can be conducted in a short amount of time. In this study, olivine single crystal and polycrystalline samples were tested using a Hysitron TI950 TriboIndenter. Temperature was varied using a cooling/heating stage from 0-175°C. Experiments were conducted under quasi-static and constant strain-rate conditions. Indentation hardness measurements were converted to uniaxial rheological properties to facilitate direct comparison with previous studies. Yield strengths for olivine range from 4.19 GPa at 175°C to 4.60 GPa at 0°C. Using various models for obstacles to dislocation motion, data are extrapolated to 0 Kelvin to extract a Peierls stress for olivine (5.32-6.45 GPa), which is at the lower end of the range of values determined in previous studies. This study demonstrates the efficacy of the nano-indentation method for the study of mineral rheology, and opens a

  10. LA-ICP-MS mapping of olivine from the Brahin and Brenham meteorites: Complex elemental distributions in the pallasite olivine precursor

    NASA Astrophysics Data System (ADS)

    McKibbin, Seann J.; O'Neill, Hugh St. C.; Mallmann, Guilherme; Halfpenny, Angela

    2013-10-01

    To investigate the early history of olivine from the Main-Group pallasites Brahin and Brenham, we have spatially mapped their trace-element distributions using laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS). Brahin olivine interiors contain ∼100-200 μm patches enriched in Cr, Al, Ti, V, Sc and Ga, separated by linear enrichments of P; these structures bear no relation to current crystal morphologies. Rather, cross-cutting relationships suggest they predate olivine-metal mixing. Brenham olivine also has internal variations for these elements. By contrast, Ni and Co concentrations in olivine from both meteorites decrease near crystal margins, as expected for freezing-in of profiles formed during diffusive re-equilibration with metal during cooling. Brenham olivine also has decreasing Al, Cr and Ti near the margin. Correlations between concentrations of Cr and Al exist for individual Brahin olivine grains, but do not hold over multiple grains, indicating a heterogeneous precursor. Al and Ti are correlated over multiple grains in Brahin, interpreted as Ti cations decorating pre-existing Al-defects. In Brenham olivine, similar geochemical trends exist, but the Cr-Al relationship probably represents both grain margin effects and pre-existing internal heterogeneity. The preservation of structure for elements which are normally fast diffusers in olivine hinges on coupled substitutions involving Al, which along with P diffuses much more slowly than most other elements under some conditions. Al concentrations in olivine are low and variable (3-33 ppm) which is inconsistent with crystallisation from a normal silicate melt; Al-in-olivine thermometers indicate that pallasite olivine was formed in a low-temperature environment. Following its delivery to the magma ocean/core-mantle boundary, Al-P systematics were not substantially modified. Assuming diffusivities for Al and P that are similar to Si (since they reside in the same crystallographic site

  11. Annealing of deformed olivine single-crystals under 'dry' conditions

    NASA Astrophysics Data System (ADS)

    Blaha, Stephan; Katsura, Tomoo

    2013-04-01

    Knowledge of rheological properties of Earth's materials is essential to understand geological processes. Open questions are the water content and crystallographic orientation dependences of dislocation creep rate, because the dominant slip system changes with increasing water content, which suggest different dislocations have different water content dependence. This project focuses on olivine, which is the most abundant mineral of the upper mantle. It is also considered to be the weakest phase and hence should control the rheology of the upper mantle. Several slip systems were reported for olivine, which are [100](010), [001](010), [001](100) and [100](001), each of which appear under different water content and stress conditions [1]. For this purpose we started to obtain data for 'dry' conditions, providing basic knowledge to understand the effect of water. Variation in dislocation creep rate according to change in physical conditions can be estimated by dislocation recovery experiments [2]. In this technique, deformed crystals are annealed, in which the dislocation density is expected to decrease due to coalescence of two dislocations. Dislocation densities are measured before and after the annealing. Dislocation mobility, which should be directly proportional to the dislocation creep rate, is estimated based on the change in dislocation density and duration of annealing. This technique has significant advantages partly because informations of strain rate and deviatoric stress, which are difficult to measure, are unnecessary, and partly because dislocation annealing is conducted under quasi-hydrostatic conditions, which allows wide ranges of P and T conditions. The first step of the experiments is to deform a single crystal of olivine. For this purpose, we developed an assembly, which deforms a single crystal in simple-shear geometry and prevent breakage, sub-grain formation and recrystallization of the crystal. Olivine single-crystals were placed in the high

  12. Kimberlitic olivines derived from the Cr-poor and Cr-rich megacryst suites

    NASA Astrophysics Data System (ADS)

    Moore, Andy; Costin, Gelu

    2016-08-01

    Reversed-zoned olivines (Fe-richer cores compared to rims), appear to be ubiquitous in kimberlites with a wide distribution. These olivines generally comprise a subordinate population relative to the dominant normally zoned olivines. However, they are notably more abundant in the megacryst-rich mid-Cretaceous Monastery and early Proterozoic Colossus kimberlites, located on the Kaapvaal and Zimbabwe cratons, respectively. The reverse-zoned olivines at these two localities define compositional fields that are closely similar to those for two olivine megacryst populations of the Cr-poor association which have been documented in the Monastery kimberlite. This points to a genetic link between megacrysts and the reversed zoned olivines. The ubiquitous, occurrence of the Fe-rich (relative to the field for rims) olivines in kimberlites with a wide geographic distribution in turn argues for an intimate link between megacrysts and the host kimberlite. Some large olivines have inclusions of rounded Cr-rich clinopyroxenes, garnets and/or spinel, characterized by fine-scale, erratic internal compositional zoning. Olivines with such chemically heterogeneous Cr-rich inclusions are not derived from disaggregated mantle peridotites, but are rather linked to the Cr-rich megacryst suite. Consequently, they cannot be used as evidence that cores of a majority of kimberlitic olivines are derived from disaggregated mantle peridotites.

  13. From olivine to ringwoodite: a TEM study of a complex process

    NASA Astrophysics Data System (ADS)

    Pittarello, Lidia; Ji, Gang; Yamaguchi, Akira; Schryvers, Dominique; Debaille, Vinciane; Claeys, Philippe

    2015-05-01

    The study of shock metamorphism of olivine might help to constrain impact events in the history of meteorites. Although shock features in olivine are well known, so far, there are processes that are not yet completely understood. In shock veins, olivine clasts with a complex structure, with a ringwoodite rim and a dense network of lamellae of unidentified nature in the core, have been reported in the literature. A highly shocked (S5-6), L6 meteorite, Asuka 09584, which was recently collected in Antarctica by a Belgian-Japanese joint expedition, contains this type of shocked olivine clasts and has been, therefore, selected for detailed investigations of these features by transmission electron microscopy (TEM). Petrographic, geochemical, and crystallographic studies showed that the rim of these shocked clasts consists of an aggregate of nanocrystals of ringwoodite, with lower Mg/Fe ratio than the unshocked olivine. The clast's core consists of an aggregate of iso-oriented grains of olivine and wadsleyite, with higher Mg/Fe ratio than the unshocked olivine. This aggregate is crosscut by veinlets of nanocrystals of olivine, with extremely low Mg/Fe ratio. The formation of the ringwoodite rim is likely due to solid-state, diffusion-controlled, transformation from olivine under high-temperature conditions. The aggregate of iso-oriented olivine and wadsleyite crystals is interpreted to have formed also by a solid-state process, likely by coherent intracrystalline nucleation. Following the compression, shock release is believed to have caused opening of cracks and fractures in olivine and formation of olivine melt, which has lately crystallized under postshock equilibrium pressure conditions as olivine.

  14. A New Spinel-Olivine Oxybarometer: Near-Liquidus Partitioning of V between Olivine-Melt, Spinel-Melt, and Spinel-Olivine in Martian Basalt Composition Y980459 as a Function of Oxygen Fugacity

    NASA Technical Reports Server (NTRS)

    Papike, J. J.; Le, L.; Burger, P. V.; Shearer, C. K.; Bell, A. S.; Jones, J.

    2013-01-01

    Our research on valence state partitioning began in 2005 with a review of Cr, Fe, Ti, and V partitioning among crystallographic sites in olivine, pyroxene, and spinel [1]. That paper was followed by several on QUE94201 melt composition and specifically on Cr, V, and Eu partitioning between pyroxene and melt [2-5]. This paper represents the continuation of our examination of the partitioning of multivalent V between olivine, spinel, and melt in martian olivine-phyric basalts of Y980459 composition [6, 7]. Here we introduce a new, potentially powerful oxybarometer, V partitioning between spinel and olivine, which can be used when no melt is preserved in the meteorite. The bulk composition of QUE94201 was ideal for our study of martian pyroxene-phyric basalts and specifically the partitioning between pyroxene-melt for Cr, V, and Eu. Likewise, bulk composition Y980459 is ideal for the study of martian olivine-phyric basalts and specifically for olivine-melt, spinel-melt, and spinel-olivine partitioning of V as a function of oxygen fugacity.

  15. Olivine Morphology and Trace Element Fractionation in Metal of Main Group Pallasites

    NASA Astrophysics Data System (ADS)

    Kissin, S. A.

    2009-05-01

    Pallasites are stony-iron meteorites consisting largely of olivine macrocrysts in a matrix of iron-nickel alloy in the form of kamacite-taenite intergrowth. Pallasites have been divided into Main Group (PMG), Eagle Station Grouplet (PES) and ungrouped (IrUn) also called pyroxene pallasites. Within PMG, six have anomalous metal contents (PMGam) and five have anomalous olivine compositions (PMGas). The morphologies of olivine macrocrysts in PMG are essentially of two types, angular or rounded. Of 19 normal PMG whose compositions and olivine morphologies are known, 17 have angular olivines. In the remaining two PMG, olivines are rounded as well as those of three PMGam and three PMGas. Experimental studies have demonstrated that rounding of olivines in molten iron-nickel alloy occurs in short times on a geological scale. Metallic cooling rates for PMG have been shown to be rapid at high temperature and slow at low temperature. Detailed analyses have demonstrated that angular olivines are compositionally zoned and therefore not in equilibrium with metal. These conditions imply that molten metal was injected into angular olivines fractured by an impact event. However, the presence of rounded olivine macrocrysts in PMGam and PMGas, as well as in two normal PMG, implies that these pallasites have retained an earlier generation of olivine. A long-standing theory for the origin of pallasites is that they represent the core-mantle boundary of a parent- body, subsequently disrupted by impact and injected by impact-melted metal. A relationship between the trace element fractionation trend in group IIIAB iron meteorites and metal of PMG is evident in that normal members cluster at the end of this fractionation trend. However, the theory does not account for the presence of rounded olivine macrocrysts. Log trace element vs log Au plots of indicate that most PMGam members exhibit the same fractionation trend as that seen for group IIIAB irons, and these correlate with PMGam and

  16. Water-induced fabrics of olivine in peridotites from the Lindas Nappe, Bergen arc, western Norway

    NASA Astrophysics Data System (ADS)

    Jung, Sejin; Jung, Haemyeong; Austrheim, Hâkon

    2010-05-01

    The Bergen Arc, western Norway is composed of several units distributed in an arc shape. Lindas Nappe is one of these units. Two peridotite outcrops in Lindas Nappe anorthosite complex were studied to understand deformation conditions of olivine. A mylonite zone was found in the peridoties and deformation fabrics of small olivine in the area were also studied. Lattice preferred orientation (LPO) of olivine was determined using the electron backscattered diffraction (EBSD) in SEM. Water content of olivine in the samples was measured using the Fourier transformation infrared (FTIR) spectroscopy. We observed three different types of LPOs (E-, B-, and A-type) of olivine in a large grain area. Sample (372) showed that [100] axes of olivine are aligned subparallel to the lineation and [001] axes aligned normal to the foliation, which is known as E-type LPO of olivine (Jung et al., 2006). Three samples (375, 380, and 381) showed that [001] axes of olivine are aligned subparallel to the lineation and [010] axes aligned normal to the foliation, which is known as B-type LPO of olivine. Another sample (379) in the large grain area showed that [100] axes of olivine are aligned subparallel to the lineation and [010] axes aligned normal to the foliation, which is known as A-type LPO of olivine. On the other hand, we observed two types of LPOs of olivine in a mylonite zone with a small grain-size: B- and C-type. C-type LPO is characterized as [001] axes of olivine aligned subparallel to the lineation and [100] axes of olivine aligned nearly normal to the foliation. Previous experimental study showed that B-, C-, and E-type LPO patterns were observed in a wet condition and A-type LPO was observed in a dry condition (Jung et al., 2006). FTIR analysis of olivine revealed that a sample showing the A-type LPO showed only small IR absorption peaks in the range of wave numbers 3000 - 3750 cm-1. In contrast, samples showing B-, C-, and E-type LPO showed large IR absorption peaks in the

  17. Enhanced olivine carbonation within a basalt as compared to single-phase experiments: the impact of redox and bulk composition on the dissolution kinetics of olivine

    NASA Astrophysics Data System (ADS)

    Sissmann, O.; Brunet, F.; Martinez, I.; Guyot, F. J.; Verlaguet, A.; Pinquier, Y.; Garcia, B.; Chardin, M.; Kohler, E.; Daval, D.

    2014-12-01

    Olivine (Mg,Fe)2SiO4, which is one of the major mineral constituents of mafic and ultramafic rocks, has an attractive potential for CO2 mineral sequestration, as it possesses a high content of carbonate-forming divalent cations and exhibits one of the highest dissolution rate amongst rock-forming minerals. This study reports drastic differences in carbonation yields between experiments performed on olivine-rich basalt samples and on olivine separates (a more restricted chemical system). Batch experiments were conducted in water at 150°C and pCO2 = 280 bars on a Mg-rich tholeiitic basalt (9.3 wt.% MgO and 12.2 wt.% CaO), composed of olivine, Ti-magnetite, plagioclase and clinopyroxene. After 45 days of reaction, 56 wt.% of the initial MgO has reacted with CO2 to form Fe-bearing magnesite (Mg0.8Fe0.2)CO3 along with minor calcium carbonates. The substantial decrease of olivine content upon carbonation supports the idea that ferroan magnesite formation mainly follows from olivine dissolution. In contrast, in experiments performed under similar run durations and P/T conditions with a San Carlos olivine separate (47.8 wt.% MgO) of similar grain size, only 5 wt.% of the initial MgO content reacted to form Fe-bearing magnesite. The overall carbonation kinetics of the basalt is enhanced by a factor of 40. It could be accounted for by differences in chemical and textural properties of the secondary-silica layer which covers reacted olivine grains in both types of sample. A TEM inspection of mineral surfaces shows that the thin amorphous silica layer (~100 nm) is porous in the case of the basalt sample and that it contains significant amounts of iron and aluminum. Thus, we propose that the composition of the olivine environment itself can strongly influence the olivine dissolution-carbonation process. Consequently, laboratory data obtained on olivine separates might yield a conservative estimate of the true carbonation potential of olivine-bearing basaltic rocks. More

  18. Deformation of Olivine at Mantle Pressure using D-DIA

    SciTech Connect

    Li,L.

    2006-01-01

    Knowledge of the rheological properties of mantle materials is critical in modeling the dynamics of the Earth. The high-temperature flow law of olivine defined at mantle conditions is especially important since the pressure dependence of rheology may affect our estimation of the strength of olivine in the Earth's interior. In this study, steady-state high-temperature (up to 1473 K) deformation experiments of polycrystalline olivine (average grain size ? 10 ?m) at pressure up to 9.6 GPa, were conducted using a Deformation-DIA (D-DIA) high-pressure apparatus and synchrotron X-ray radiation. The oxygen fugacity (fo2) during the runs was in-between the iron-wustite and the Ni/NiO buffers' fo2. The water content of the polycrystalline samples was generally about 150 to 200 wt. ppm but was as low as 35 wt ppm. Typically, 30 % strain was generated during the uniaxial compression. Sample lengths during the deformation process as well as the differential stresses were monitored in situ by X-ray radiography and diffraction, respectively. The strain rate was derived with an accuracy of 10?6 s?1. Differential stress was measured at constant strain rate (?10?5 s?1) using a multi-element solid-state detector combined with a conical slit. Recovered specimens were investigated by optical and transmission electron microscopy (TEM). TEM shows that dislocation glide was the dominant deformation mechanism throughout the experiment. Evidence of dislocation climb and cross-slip as active mechanisms are also reported. Deformation data show little or no dependence of the dislocation creep flow with pressure, yielding to an activation volume V* of 0 {+-} 5 cm3/mol. These new data are consistent with the high-temperature rheological laws at lower pressures, as reported previously.

  19. Deformation of olivine single crystals under lithospheric conditions

    NASA Astrophysics Data System (ADS)

    Demouchy, S.; Tommasi, A.; Cordier, P.

    2012-12-01

    The rheology of mantle rocks at lithospheric temperatures (<1000°C) remains poorly constrained, in contrast to the extensive experimental data on creep of olivine single crystals and polycrystalline aggregates at high temperature (T > 1200°C). Consequently, we have performed tri-axial compression experiments on oriented single crystals and polycrystalline aggregates of San Carlos olivine at temperatures ranging from 800° to 1090°C. The experiments were carried out at a confining pressure of 300 MPa in a high-resolution gas-medium mechanical testing apparatus at constant strain rates ranging from 7 × 10-6 s-1 to 1 × 10-4 s-1 . Compression was applied along three different crystallographic directions: [101]c, [110]c and [011]c, to activate the several slip systems. Yield differential stresses range from 88 to 1076 MPa. To constrain hardening, stick-and-slip, or strain localization behaviors, all samples were deformed at constant displacement rate for finite strains between 4 to 23 %. Hardening was observed in all experiments and the maximum differential stress often overcame the confining pressure. EBSD mapping highlights macroscale bending of the crystalline network in three crystals. TEM observations on several samples show dislocations with [100] and [001] Burgers vectors in all samples, but dislocation arrangements vary. The results from the present study permit to refining the power-law expressing the strain rate dependence on stress and temperature for olivine, allowing its application to the lithospheric mantle. Our experiments confirm that previous published high-temperature power flow laws overestimate the strength of lithospheric mantle and that the transition to low-temperature creep occurs at higher temperatures than it has previously been established.

  20. LIME silicates in amoeboid olivine aggregates in carbonaceous chondrites: Indicator of nebular and asteroidal processes

    NASA Astrophysics Data System (ADS)

    Komatsu, Mutsumi; Fagan, Timothy J.; Mikouchi, Takashi; Petaev, Michail I.; Zolensky, Michael E.

    2015-07-01

    MnO/FeO ratios in olivine from amoeboid olivine aggregates (AOAs) reflect conditions of nebular condensation and can be used in concert with matrix textures to compare metamorphic conditions in carbonaceous chondrites. LIME (low-iron, Mn-enriched) olivine was identified in AOAs from Y-81020 (CO3.05), Kaba (CV~3.1), and in Y-86009 (CV3), Y-86751 (CV3), NWA 1152 (CR/CV3), but was not identified in AOAs from Efremovka (CV3.1-3.4) or Allende (CV>3.6). According to thermodynamic models of nebular condensation, LIME olivine is stable at lower temperatures than Mn-poor olivine and at low oxygen fugacities (dust enrichment <10× solar). Although this set of samples does not represent a single metamorphic sequence, the higher subtypes tend to have AOA olivine with lower Mn/Fe, suggesting that Mn/Fe decreases during parent body metamorphism. Y-81020 has the lowest subtype and most forsteritic AOA olivine (Fo>95) in our study, whereas Efremovka AOAs are slightly Fe-rich (Fo>92). AOA olivines from Kaba are mostly forsteritic, but rare Fe-rich olivine precipitated from an aqueous fluid. A combination of precipitation of Fe-rich olivine and diffusion of Fe into primary olivine grains resulted in iron-rich compositions (Fo97-59) in Allende AOAs. Variations from fine-grained, nonporous matrix toward higher porosity and coarser lath-like matrix olivine can be divided into six stages represented by (1) Y-81020, Efremovka, NWA 1152; (2) Y-86751 lithology B; (3) Y-86009; (4) Kaba; (5) Y-86751 lithology A; (6) Allende. These stages are inferred to represent general degree of metamorphism, although the specific roles of thermally driven grain growth and diffusion versus aqueous dissolution and precipitation remain uncertain.

  1. Serpentinization and alteration in an olivine cumulate from the Stillwater Complex, Southwestern Montana

    USGS Publications Warehouse

    Page, N.J.

    1976-01-01

    Some of the olivine cumulates of the Ultramafic zone of the Stillwater Complex, Montana, are progressively altered to serpentine minerals and thompsonite. Lizardite and chrysotile developed in the cumulus olivine and postcumulus pyroxenes; thompsonite developed in postcumulus plagioclase. The detailed mineralogy, petrology, and chemistry indicate that olivine and plagioclase react to form the alteration products, except for H2O, without changes in the bulk composition of the rocks. ?? 1976 Springer-Verlag.

  2. [Study on the FTIR spectra of OH in olivines from mengyin kimberlite].

    PubMed

    Ai, Qun; Yang, Zhi-jun; Zeng, Xiang-qing; Zheng, Yun-long; Hu, Piao-ye

    2013-09-01

    The results of FTIR spectra study of OH in olivines from Mengyin kimberlite show that there are more than 60 OH absorption peaks in the range of 3800-3000 cm(-1). We identified four major spectral features in the OH absorption bands of kimberlitic olivines. One is with nuOH in the range of 3800-3700 cm(-1), which is caused by the vapour of the room circumstance, and can not be regarded as intrinsic or non-intrinsic nuOH of the olivines. Another one is with nuOH in the range of 3710-3620 cm(-1), which belongs to three "water"-bearing minerals including serpentine, talc and Mg-bearing amphiboles, which is the non-intrinsic nuOH of the olivines. There is the possibility that H in hydrous minerals mainly entered into olivines during post-emplacement processes of the kimberlite magma. The third one is with nuOH in the range of 3620-3425 cm(-1), which originated from H occupying the Si-defect in the olivine structure, forming humite-like defects, and/or the defects that H occupies (Mg,Fe)-depletion, which is certainly attributed to the intrinsic nuOH of the olivines. In this case, H possibly entered into olivines following its immersion in the high temperature and rich fluid kimberlite magma in the mantle circumstance. The last one is with nuOH in the range of 3425-3000 cm(-1). In this area, nuOH is assigned to fluid inclusions of the olivines, and is the non-intrinsic nuOH of olivines. Fluid inclusions can enter into the olivines either during post-emplacement processes of the kimberlite magma or during the periods that olivines were formed in the mantle.

  3. [Study on the FTIR spectra of OH in olivines from mengyin kimberlite].

    PubMed

    Ai, Qun; Yang, Zhi-jun; Zeng, Xiang-qing; Zheng, Yun-long; Hu, Piao-ye

    2013-09-01

    The results of FTIR spectra study of OH in olivines from Mengyin kimberlite show that there are more than 60 OH absorption peaks in the range of 3800-3000 cm(-1). We identified four major spectral features in the OH absorption bands of kimberlitic olivines. One is with nuOH in the range of 3800-3700 cm(-1), which is caused by the vapour of the room circumstance, and can not be regarded as intrinsic or non-intrinsic nuOH of the olivines. Another one is with nuOH in the range of 3710-3620 cm(-1), which belongs to three "water"-bearing minerals including serpentine, talc and Mg-bearing amphiboles, which is the non-intrinsic nuOH of the olivines. There is the possibility that H in hydrous minerals mainly entered into olivines during post-emplacement processes of the kimberlite magma. The third one is with nuOH in the range of 3620-3425 cm(-1), which originated from H occupying the Si-defect in the olivine structure, forming humite-like defects, and/or the defects that H occupies (Mg,Fe)-depletion, which is certainly attributed to the intrinsic nuOH of the olivines. In this case, H possibly entered into olivines following its immersion in the high temperature and rich fluid kimberlite magma in the mantle circumstance. The last one is with nuOH in the range of 3425-3000 cm(-1). In this area, nuOH is assigned to fluid inclusions of the olivines, and is the non-intrinsic nuOH of olivines. Fluid inclusions can enter into the olivines either during post-emplacement processes of the kimberlite magma or during the periods that olivines were formed in the mantle. PMID:24369634

  4. Chromium valences in ureilite olivine and implications for ureilite petrogenesis

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Sutton, S. R.; Wirick, S.; Jercinovic, M. J.

    2013-12-01

    Ureilites are a group of ultramafic achondrites commonly thought to be residues of partial melting on a carbon-rich asteroid. They show a large variation in FeO content (olivine Fo values ranging from ∼74 to 95) that cannot be due to igneous fractionation and suggests instead variation in oxidation state. The presence of chromite in only a few of the most ferroan (Fo 75-76) samples appears to support such a model. MicroXANES analyses were used in this study to determine the valence states of Cr (previously unknown) in olivine cores of 11 main group ureilites. The goal of this work was to use a method that is independent of Fo to determine the oxidation conditions under which ureilites formed, in order to evaluate whether the ureilite FeO-variation is correlated with oxidation state, and whether it is nebular or planetary in origin. Two of the analyzed samples, LEW 88774 (Fo 74.2) and NWA 766 (Fo 76.7) contain primary chromite; two others, LAP 03587 (Fo 74.4) and CMS 04048 (Fo 76.2) contain sub-micrometer-sized exsolutions of chromite + Ca-rich pyroxene in olivine; and one, EET 96328 (Fo 85.2) contains an unusual chromite grain of uncertain origin. No chromite has been observed in the remaining six samples (Fo 77.4-92.3). Chromium in olivine in all eleven samples was found to be dominated by the divalent species, with valences ranging from 2.10 ± 0.02 (1σ) to 2.46 ± 0.04. The non-chromite-bearing ureilites have the most reduced Cr, with a weighted mean valence of 2.12 ± 0.01, i.e., Cr2+/Cr3+ = 7.33. All low-Fo chromite-bearing ureilites have more oxidized Cr, with valences ranging from 2.22 ± 0.03 to 2.46 ± 0.04. EET 96328, whose chromite grain we interpret as a late-crystallizing phase, yielded a reduced Cr valence of 2.15 ± 0.07, similar to the non-chromite-bearing samples. Based on the measured Cr valences, magmatic (1200-1300 °C) oxygen fugacities (fO2) of the non-chromite-bearing samples were estimated to be in the range IW-1.9 to IW-2.8 (assuming

  5. Effect of Water on High Pressure Olivine Slip Systems Activity

    NASA Astrophysics Data System (ADS)

    Girard, J.; Chen, J.; Raterron, P. C.; Holyoke, C. W.

    2012-12-01

    Seismologic studies of the Earth's shallow (Z<220 km) upper mantle have observed seismic anisotropy parallel to the direction of plate movement and have related this observation to alignment of olivine [100] due to shearing related to convection. These observations have been reinforced by field-based and experimental investigations which observe evidence that [100] slip is dominant at low pressures and water contents. However, direct evidence of the dominant slip system in the deep upper mantle (Z>220 km) is limited to a few studies of xenoliths which have LPOs consistent with [001] slip. Experimental studies of dry single crystals and polycrystals indicate that [001] slip becomes dominant at pressures > 8 GPa. However, water contents in the mantle are significant (~1000 H/106 Si) and we do not know how the slip systems of olivine are affected by higher water contents at high pressures. In order to investigate the effect of pressure on slip systems activities in olivine deformed in wet conditions, deformation experiments were carried out on single crystals, at pressure ranging from 4 to 8 GPa and temperature between 1373 and 1473 K in the Deformation-DIA apparatus (D-DIA) of the X17B2 beamline of the NSLS (NY, USA). Specimen were deformed in uniaxial compression along [110]c, [011]c and [101]c crystallographic directions, promoting the activation of, respectively, [100](010), [001](010) slip systems, and simultaneously [100](001) and [001](100) slip systems. Talc sleeves about the annulus of the single crystals were used as source of water during deformation. In addition, run products investigation using a micro-focused IR beam at the U2 beamline enables accurate mapping of the water content across the deformed single crystals using FTIR spectroscopy, while specimen deformation microstructures were investigated by TEM. We observe a slip-system transition in wet specimen occurring at lower pressure than that observed by Raterron et al. (2007) in dry specimens. For

  6. Origin of graphitic carbon and pentlandite in matrix olivines in the Allende meteorite.

    PubMed

    Brearley, A J

    1999-08-27

    Matrix olivines in the Allende carbonaceous chondrite are believed to have formed by condensation processes in the primitive solar nebula. However, transmission electron microscope observations of numerous matrix olivines show that they contain abundant, previously unrecognized, nanometer-sized inclusions of pentlandite and poorly graphitized carbon. Neither of these phases would have been stable at the high-temperature conditions required to condense iron-rich olivine in the solar nebula. The presence of these inclusions is consistent with formation of the olivines by parent body processes that involved overgrowth of fine-grained organic materials and sulfides in the precursor matrix materials.

  7. Relation of the spectroscopic reflectance of olivine to mineral chemistry and some remote sensing implications.

    USGS Publications Warehouse

    King, T.V.V.; Ridley, W.I.

    1987-01-01

    Using high-resolution visible and near-infrared diffuse spectral reflectance, systematically investigates apparent wavelength shifts as a function of mineral chemistry in the Fe/Mg olivine series from Fo11 to Fo91. The study also shows that trace amounts of nickel can be spectrally detected in the olivine structure. Significant spectral variation as a function of grain size is also demonstrated, adding a further complication to the interpretation of remotely sensed data from olivine-rich surfaces. Some permutations of Fe-Mg-Ni relations in olivines are discussed as they apply to the interpretation of asteroid surfaces and other extraterrestrial bodies. -from Authors

  8. Magmatic history and parental melt composition of olivine-phyric shergottite LAR 06319: Importance of magmatic degassing and olivine antecrysts in Martian magmatism

    NASA Astrophysics Data System (ADS)

    Balta, J. Brian; Sanborn, Matthew; McSween, Harry Y.; Wadhwa, Meenakshi

    2013-08-01

    Several olivine-phyric shergottites contain enough olivine that they could conceivably represent the products of closed-system crystallization of primary melts derived from partial melting of the Martian mantle. Larkman Nunatak (LAR) 06319 has been suggested to represent a close approach to a Martian primary liquid composition based on approximate equilibrium between its olivine and groundmass. To better understand the olivine-melt relationship and the evolution of this meteorite, we report the results of new petrographic and chemical analyses. We find that olivine megacryst cores are generally not in equilibrium with the groundmass, but rather have been homogenized by diffusion to Mg# 72. We have identified two unique grain types: an olivine glomerocryst and an olivine grain preserving a primary magmatic boundary that constrains the time scale of eruption to be on the order of hours. We also report the presence of trace oxide phases and phosphate compositions that suggest that the melt contained approximately 1.1% H2O and lost volatiles during cooling, also associated with an increase in oxygen fugacity upon degassing. We additionally report in situ rare earth element measurements of the various mineral phases in LAR 06319. Based on these reported trace element abundances, we estimate the oxygen fugacity in the LAR 06319 parent melt early in its crystallization sequence (i.e., at the time of crystallization of the low-Ca and high-Ca pyroxenes), the rare earth element composition of the parent melt, and those of melts in equilibrium with later formed phases. We suggest that LAR 06319 represents the product of closed-system crystallization within a shallow magma chamber, with additional olivine accumulated from a cumulate pile. We infer that the olivine megacrysts are antecrysts, derived from a single magma chamber, but not directly related to the host magma, and suggest that mixing of antecrysts within magma chambers may be a common process in Martian magmatic

  9. TEMPERATURE-DEPENDENT INFRARED OPTICAL CONSTANTS OF OLIVINE AND ENSTATITE

    SciTech Connect

    Zeidler, S.; Mutschke, H.; Posch, Th. E-mail: harald.mutschke@uni-jena.de

    2015-01-10

    Since the Infrared Space Observatory (ISO) mission, it has become clear that dust in circumstellar disks and outflows consists partly of crystalline silicates of pyroxene and olivine type. An exact mineralogical analysis of the dust infrared emission spectra relies on laboratory spectra, which, however, have been mostly measured at room temperature so far. Given that infrared spectral features depend on the thermal excitation of the crystal's vibrational modes, laboratory spectra measured at various (low and high) temperatures, corresponding to the thermal conditions at different distances from the star, can improve the accuracy of such analyses considerably. We have measured the complex refractive index in a temperature range of 10-973 K for one mineral of each of those types of silicate, i.e., for an olivine and an enstatite of typical (terrestrial) composition. Thus, our data extend the temperature range of previous data to higher values and the compositional range to higher iron contents. We analyze the temperature dependence of oscillator frequencies and damping parameters governing the spectral characteristics of the bands and calculate absorption cross-sectional spectra that can be compared with astronomical emission spectra. We demonstrate the usefulness of our new data by comparing spectra calculated for a 100 K dust temperature with the ISO SWS spectrum of IRAS 09425-6040.

  10. Thermoelasticity of olivine to 8 GPa 1073K

    SciTech Connect

    Liu,W.; Li, B.

    2006-01-01

    In situ synchrotron X-ray diffraction measurements have been carried out on San Carlos olivine (Mg0.9Fe0.1)2SiO4 up to 8 GPa and 1073 K. Data analysis using the high-temperature Birch-Murnaghan (HTBM) equation of state (EoS) yields the temperature derivative of the bulk modulus ({partial_derivative}KT/{partial_derivative}T)P = -0.019 {+-} 0.002 GPa K-1. The thermal pressure (TH) approach gives aKT = 4.08 {+-} 0.10 x 10-3 GPa K-1, from which ({partial_derivative}KT/{partial_derivative}T)P = -0.019 {+-} 0.001 GPa K-1 is derived. Fitting the present data to the Mie-Grueneisen-Debye (MGD) formalism, the Grueneisen parameter at ambient conditions 0 is constrained to be 1.14 {+-} 0.02 with fixed volume dependence q = 1. Combining the present data with previous results on iron-bearing olivine and fitting to MGD EoS, we obtain 0 = 1.11 {+-} 0.01 and q = 0.54 {+-} 0.36. In this study the thermoelastic parameters obtained from various approaches are in good agreement with one another and previous results.

  11. Nickeliferous sulfides in xenoliths, olivine megacrysts and basaltic glass

    NASA Astrophysics Data System (ADS)

    Fleet, Michael E.; Stone, William E.

    1990-11-01

    The composition of olivine and nickeliferous sulfide inclusions from a selection of mafic and ultramafre rocks, xenoliths and megacrysts, including picritic basalts from Kilauea Volcano, Hawaii, kimberlite from Fayette County, Pennsylvania, and megacrysts from Mount Shasta, California are compared with the mean experimental value of the distribution coefficient for Ni/Fe exchange (KD3=32). Only nine of the forty five olivipe/bulk-sulfide pairs investigated have compositions consistent with equilibration at high temperature, yielding calculated KD3 values in the range 22 to 41. The remaining pairs have calculated KD3 values which range from 0 to 19. Bulk-sulfides in disequilibrated assem-blages are consistently depleted in nickel and within both indivudual associations and individual petrographic sections they exhibit a wide variation in NiS content. The bulk copper contents of olivine-and groundmass-hosted sulfides from Kilauea Volcano range from 0.5 to 43 at%, and samples from the Kilauea Iki lava lake are more Fe-and Cu-rich and generally have lower KD3 values than those from the eruption itself. As with magmatic Ni-Cu sulfide deposits, most nickeliferous sulfide inclusions in mantle-related rocks and xenoliths and in volcanic rocks do not have pristine early-magmatic bulk compositions, and it would seem to be premature to attribute these sulfides solely to either a mantle or an early-magnatic origin.

  12. Serpentinization of Olivine by Seawater: A Flow-Through Experiment

    NASA Astrophysics Data System (ADS)

    Gouze, P.; Luquot, L.; Andreani, M.; Godard, M.; Gibert, B.

    2011-12-01

    The mantle exposed at slow spreading ridges is pervasively serpentinized, down to ca. 5km according to geophysical data. The onset and durability of this hydration process require efficient penetration and renewal of fluids at the mineral-fluid interface. However, the mechanisms of fluid penetration are still poorly understood. Moreover, serpentinization is exovolumic, if a mass-conservative system is assumed, or chemical elements are leached out to conserve rock volume. Thus, the extent of serpentinization depends of the system capacity to create space and/or to drive mass transfers. In order to investigate these hydrodynamic and chemical mechanisms, we did a laboratory experiment during which seawater was injected in a sintered San Carlos olivine sample at conditions representative of low temperature ultramafic hydrothermal systems. The percolation-reaction experiment was carried out at 19 MPa and 190°C; the initial water flow was set at 0.2 mL/h then decreased down to 0.06 mL/h after 8 days. During the experiment (23 days), permeability decreased continuously. The composition of the outlet fluid varied strongly during the first 24h of the experiment, then reached equilibrium values. The high Si concentrations in outlet fluids indicated steady olivine dissolution, while their low Fe and Mg concentrations suggested precipitation of Fe- and Mg-rich mineral phases. The reacted sample acquired a reddish brown color, indicating oxidation reactions occurred. Optical observation and SEM imaging revealed the presence of a soft white material filling the pores of the reacted sample. It was identified as a poorly crystallized serpentine type material by AEM/TEM analyses. This proto-serpentine is intimately associated to <100 nm Fe-oxide patches (probably hematite) growing on the olivine surface. We interpret the precipitation of this proto-serpentine together with Fe-oxides throughout the sample as marking the early stages of serpentinization. The fluid composition not

  13. Phosphorus as indicator of magmatic olivine residence time, morphology and growth rate

    NASA Astrophysics Data System (ADS)

    Sobolev, Alexander; Batanova, Valentina

    2015-04-01

    Phosphorus is among of slowest elements by diffusion rate in silicate melts and crystals (e.g. Spandler et al, 2007). In the same time it is moderately incompatible to compatible with olivine (Brunet & Chazot, 2001; Grant & Kohn, 2013). This makes phosphorus valuable tracer of olivine crystallization in natural conditions. Indeed, it is shown that natural magmatic olivine crystals commonly posses strong and complicated zoning in phosphorus (Milman-Barris et al, 2008; Welsch et al, 2014). In this paper we intend to review phosphorus behavior in olivine in published experimental and natural olivine studies and present large set of new EPMA data on phosphorus zoning in olivine phenocrysts from MORBs, OIBs, komatiites and kimberlites. We will show that sharp olivine zones enriched in phosphorus by a factor of 10-20 over prediction by equilibrium partition may be due to formation of P-rich boundary layer on the interface of fast growing olivine. This is proved by finding of small-size (normally 10 mkm or less) exceptionally P-rich melt inclusions in olivine, which are otherwise similar in composition to typical melt. These observations could provide potential olivine growth speedometer. We will also demonstrate, that sharp zoning in phosphorus may provide valuable information on the residence time of olivine crystals in different environments: magma chambers and conduits as well as mantle sources. This study has been founded by Russian Science Foundation grant 14-17-00491. References: Spandler, et al, 2007, Nature, v. 447, p. 303-306; Brunet & Chazot, 2001, Chemical Geology, v. 176, p. 51-72; Grant & Kohn, 2013, American Mineralogist, v. 98, p. 1860-1869; Milman-Barris et al, 2008, Contr. Min. Petrol. v. 155, p.739-765; Welsch et al, 2014, Geology, v. 42, p.867-870.

  14. A Luna 20 Troctolite Fragment with P-Bearing Olivine: A Missing Component?

    NASA Astrophysics Data System (ADS)

    Demidova, S. I.; Nazarov, M. A.; Ryazantsev, K. M.; Kononkova, N. N.; Brandstätter, F.; Ntaflos, Th.

    2016-08-01

    P-bearing mineral phases in lunar rocks are mainly phosphates. However P may be concentrated in lunar olivines as well. Here we report on a first find of P-bearing olivine in a pyroxene troctolite fragment from the Luna 20 site.

  15. Olivine-mica pyroxenite xenoliths from northern Tanzania: metasomatic products of upper-mantle peridotite

    NASA Astrophysics Data System (ADS)

    Dawson, J. B.; Smith, J. V.

    1992-04-01

    Olivine-mica-pyroxene blocks in Neogene pyroclastics from Oldoinyo Lengai and Loluni, Tanzania, result from K, Ca, Fe, Ti, Al, REE, Cl, F and OH metasomatism of upper-mantle peridotite. Deformed olivine relicts and high Cr and Ni in bulk-rock analyses indicate a peridotite precursor.

  16. Systematics of Ni, Co, Cr and V in Olivine from Planetary Melt Systems: Martian Basalts

    NASA Technical Reports Server (NTRS)

    Herd, C. D. K.; Jones, J. H.; Shearer, C. K.; Papike, J. J.

    2001-01-01

    Secondary Ion Mass Spectrometry (SIMS) data for Ni, Co, Cr, and V in olivine in martian basalts is compared to data from lunar and terrestrial basalts. We use experimentally-derived and published D values to calculate as-yet unsampled, olivine-bearing, non-cumulus melt compositions. Additional information is contained in the original extended abstract.

  17. Termination and hydration of forsteritic olivine (0 1 0) surface

    NASA Astrophysics Data System (ADS)

    Yan, Hongping; Park, Changyong; Ahn, Gun; Hong, Seungbum; Keane, Denis T.; Kenney-Benson, Curtis; Chow, Paul; Xiao, Yuming; Shen, Guoyin

    2014-11-01

    Termination and hydration of the forsteritic (Fo90Fa10) olivine (0 1 0) surface have been investigated with high-resolution specular X-ray reflectivity and Atomic Force Microscopy. The surface was prepared by polishing a naturally grown {0 1 0} face, from which we found the polished surface in acidic (pH 3.5) alumina suspension exhibits regular steps while the basic (pH 9.5) silica polished surface is irregularly roughened, indicating there are two distinguishable mechanochemical processes for the surface dissolution. The quantitative interpretation of the regular steps from the alumina-polished surface suggests that the observed step heights correspond to multiples of crystallographic unit cell. Only this atomically terraced surface is investigated with the high-resolution X-ray reflectivity (HRXR) to determine the surface termination and hydration. The basic silica paste polished surface turned out too rough to measure with X-ray reflectivity. HRXR reveals that the alumina polished olivine (0 1 0) surface in pure water is terminated at a plane including half-occupied metal ion sites (M1), an oxygen vacancy site, and a silicate tetrahedral unit with one of its apices pointing outward with respect to the surface. An ideal termination with the oxygen vacancy would fulfill the stoichiometry of the formula unit; however, in the observation, the vacancy site is filled by an adsorbed water species and about a quarter of the remaining metal ions are further depleted. The terminating plane generates two distinct atomic layers in the laterally averaged electron density profile, on which two highly ordered adsorbed water layers are formed. The first layer formation is likely through the direct interaction with the M1 plane and the second layer is likely through the hydrogen bonding interaction with the first water layer. With this multilayered adsorbed water structure, the surface metal ion is partially hydrated by the vacancy-filling water species and adsorbed water

  18. Fine, nickel-poor Fe-Ni grains in the olivine of unequilibrated ordinary chondrites

    NASA Astrophysics Data System (ADS)

    Rambaldi, E. R.; Wasson, J. T.

    1982-06-01

    Nickel-poor Fe-Ni grains smaller than 2.0 microns are common inclusions in ordinary, unequilibrated chondrites' porphyritic chondrule olivine, where the olivine grains seem to be relicts that survived chondrule formation without melting. This 'dusty' metal, whose most common occurrence is in the core of olivine grains having clear, Fe-poor rims, appears to be the product of the in situ reduction of FeO from the host olivine, with H2 or carbonaceous matter being the most likely reductants. H2 may have been implanted by solar wind or solar flare irradiation, but this requires the dissipation of nebular gas before the end of the chondrule formation process. Carbonaceous matter may have been implanted by shock. The large relict olivine grains may be nebular condensates or fragments broken from earlier chondrule generations.

  19. The Mn-Fe negative correlation in olivines in ALHA 77257 ureilite

    NASA Technical Reports Server (NTRS)

    Miyamoto, M.; Furuta, T.; Fujii, N.; Mckay, D. S.; Lofgren, G. E.; Duke, M. B.

    1993-01-01

    An electron probe microanalyzer is used to measure the Mn, Fe, and oxygen zoning profiles of olivines in the ALHA 77257 ureilite. This is done to study the effects of reduction on the Mn-Fe value, as ureilite olivines exhibit thin reduced rims. Since the Mn content gradually increases toward the rim of ureilite olivines, while the Fa (= 100 x Fe/(Mg + Fe), mol percent) component decreases, the Mn-Fe content of olivine is likely related to redox conditions. The results of melting experiments suggest that the Mn-Fe positive correlation is related to temperature and that the negative correlation of Mn-Fe in olivine and low-Ca pyroxene is related to reduction.

  20. Origin of plagioclase-olivine inclusions in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Sheng, Y. J.; Hutcheon, I. D.; Wasserburg, G. J.

    1991-02-01

    The origin of plagioclase-olivine inclusions (POIs) from three CV chondrites and one ungrouped chondrite was investigated by examining the chemical, mineralogical, and isotopic characteristics of a group of POIs from these chondrites. Results of these analyses demonstrate that the mixing and the partial melting processes in these inclusions were superimposed on more ancient isotopically heterogeneous material. A comparison of the essential characteristics of POIs and CAIs suggests that the major processes leading to the formation of POIs (such as condensation, dust/gas fractionation, aggregation of chemically and isotopically disparate materials, and partial melting) are common to most CAIs and chondrules. A scenario for the origin of POIs is proposed, showing that the homogeneity of the final assemblage (whether a POI, a CAI, or a chondrite) is primarily a reflection of the thermal history rather than the nature of precursor materials.

  1. Serpentinization of Sintered Olivine during Seawater Percolation Experiments

    NASA Astrophysics Data System (ADS)

    Luquot, L.; Andreani, M.; Godard, M.; Gouze, P.; Gibert, B.; Lods, G.

    2010-12-01

    Hydration of the mantle lithosphere exposed at slow spreading ridges leads to significant changes of the rock rheological, geophysical, mineralogical and geochemical properties, and to the production of large amounts of H2 and CH4, and of complex carbon molecules that support primitive ecosystems. The onset and efficiency of these hydrothermal processes requires penetration and renewal of fluids at the mineral-fluid interface. However, the mechanisms and the depth of fluid penetration are still poorly understood. Moreover, serpentinization is exovolumic, if a mass-conservative system is assumed, or chemical elements are leached out to conserve rock volume. Thus, the durability and extent of serpentinisation depends of the system capacity to create space and/or to drive mass transfers. In order to investigate these hydrodynamic and chemical mechanisms, we did a series of laboratory experiments during which seawater was injected in sintered San Carlos olivine samples at conditions representative of low temperature ultramafic hydrothermal systems. The percolation-reaction experiments were carried out using the ICARE 2 experimental bench at a confined pressure of 19 MPa and a temperature of 190°C; water flow was set at a constant specific discharge of 0.06 mL/h. During experiments (up to 23 days), permeability decreases continuously although the high Si concentrations in outlet fluids indicate steady olivine dissolution. Fluids are also depleted in Fe and Mg, suggesting precipitation of Fe- and Mg-rich mineral phases; SEM and AEM/TEM analyses of the reacted samples allowed to characterize hematite and poorly crystallized serpentine, both formed at the expense of olivine. Mass balance calculations indicate that, on average, 15 wt. % olivine was dissolved while the same mass of serpentine (+/- brucite) was formed; concurrently, porosity decreased from ~ 12% to 5 %. We infer that the structure of the newly formed serpentine resulted in the clogging of fluid paths and

  2. Collisional Processing of Comet Surfaces: Impact Experiments into Olivine

    NASA Technical Reports Server (NTRS)

    Lederer, S. M.; Jensen, E. A.; Cintala, M. J.; Smith, D. C.; Nakamura-Messenger, K.; Keller, L. P.; Wooden, D. H.; Fernandez, Y. R.; Zolensky, M. E.

    2011-01-01

    A new paradigm has emerged where 3.9 Ga ago, a violent reshuffling reshaped the placement of small bodies in the solar system (the Nice model). Surface properties of these objects may have been affected by collisions caused by this event, and by collisions with other small bodies since their emplacement. In addition, objects in the Kuiper Belt are believed to undergo extensive collisional processing while in the Kuiper Belt. Physical manifestations of shock effects (e.g., planar dislocations) in minerals typically found in comets will be correlated with spectral changes (e.g. reddening, loss and shift of peaks, new signatures) to allow astronomers to better understand geophysical impact processing that has occurred on small bodies. Targets will include solid and granular olivine (forsterite), impacted over a range of impact speeds with the Experimental Impact Laboratory at NASA JSC. Analyses include quantification of the dependence of the spectral changes with respect to impact speed, texture of the target, and temperature.

  3. The distribution of olivine in the crater Copernicus

    NASA Technical Reports Server (NTRS)

    Lucey, Paul G.; Hawke, B. R.; Horton, Keith

    1991-01-01

    Multispectral imaging in the visible and near-IR at four wavelengths (0.73, 0.96, 1.45, and 1.99 micron) of Copernicus crater has been used to map the distribution of olivine-rich, pyroxene-poor material known previously to occur in the central peak complex. Three additional portions of the crater exhibit spectral characteristics similar to those of the central peaks, strongly suggesting the presence of material similar to that exposed in the central peaks. These areas are a scarp forming a portion of the northern rim of Copernicus, and two slump blocks in the north wall which may have been derived from the same portion of the ejecta now exposed in the rim scarp. These occurrences decrease the minimum allowable depth for this unusual material in the Copernicus target site though still represent some of the deepest material exposed by Copernicus.

  4. Infrared spectra of olivine polymorphs - Alpha, beta phase and spinel

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.

    1980-01-01

    The infrared absorption spectra of several olivines (alpha phase) and their corresponding beta phase (modified spinel) and spinel (gamma) high-pressure polymorphs are determined. Spectra were measured for ground and pressed samples of alpha and gamma A2SiO4, where A = Fe, Ni, Co; alpha and gamma Mg2GeO4; alpha Mg2SiO4; and beta Co2SiO4. The spectra are interpreted in terms of internal, tetrahedral and octagonal, and lattice vibration modes, and the spinel results are used to predict the spectrum of gamma Mg2SiO4. Analysis of spectra obtained from samples of gamma Mg2GeO4 heated to 730 and 1000 C provides evidence that partial inversion could occur in silicate spinels at elevated temperatures and pressures.

  5. In situ observation of crystallographic preferred orientation of deforming olivine at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Ohuchi, Tomohiro; Nishihara, Yu; Seto, Yusuke; Kawazoe, Takaaki; Nishi, Masayuki; Maruyama, Genta; Hashimoto, Mika; Higo, Yuji; Funakoshi, Ken-ichi; Suzuki, Akio; Kikegawa, Takumi; Irifune, Tetsuo

    2015-06-01

    Simple-shear deformation experiments on polycrystalline olivine and olivine single-crystal were conducted at pressures of 1.3-3.8 GPa and temperatures of 1223-1573 K to understand the achievement of steady-state fabric strength and the process of dynamic recrystallization. Development of crystallographic preferred orientation (CPO) of olivine was evaluated from two-dimensional X-ray diffraction patterns, and shear strain was measured from X-ray radiographs. The steady-state fabric strength of the A-type fabric was achieved within total shear strain of γ = 2. At strains higher than γ = 1, an increase in concentration of the [0 1 0] axes mainly contributes to an increase in fabric strength. At strains higher than γ = 2, the magnitude of VSH/VSV (i.e., ratio of horizontally and vertically polarized shear wave velocities) scarcely increased in most of the runs. The VSH/VSV of peridotite (70 vol.% olivine + 30 vol.% minor phases) having the steady-state A-type olivine fabric coincides with that of recent global one-dimensional models under the assumption of horizontal flow, suggesting that the seismic anisotropy observed in the shallow upper mantle is mostly explained by the development of A-type olivine fabric. Experimental results on the deformation of single-crystal olivine showed that the CPO of olivine is influenced by the initial orientation of the starting single crystal because strain is concentrated in the recrystallized areas and the relic of the starting single crystal remains. In the upper mantle, the old CPO of olivine developed in the past may affect the olivine CPO developed in the present.

  6. Remote compositional analysis of lunar olivine-rich lithologies with Moon Mineralogy Mapper (M3) spectra

    USGS Publications Warehouse

    Isaacson, P.J.; Pieters, C.M.; Besse, S.; Clark, R.N.; Head, J.W.; Klima, R.L.; Mustard, J.F.; Petro, N.E.; Staid, M.I.; Sunshine, J.M.; Taylor, L.A.; Thaisen, K.G.; Tompkins, S.

    2011-01-01

    A systematic approach for deconvolving remotely sensed lunar olivine-rich visible to near-infrared (VNIR) reflectance spectra with the Modified Gaussian Model (MGM) is evaluated with Chandrayaan-1 Moon Mineralogy Mapper (M 3) spectra. Whereas earlier studies of laboratory reflectance spectra focused only on complications due to chromite inclusions in lunar olivines, we develop a systematic approach for addressing (through continuum removal) the prominent continuum slopes common to remotely sensed reflectance spectra of planetary surfaces. We have validated our continuum removal on a suite of laboratory reflectance spectra. Suites of olivine-dominated reflectance spectra from a small crater near Mare Moscoviense, the Copernicus central peak, Aristarchus, and the crater Marius in the Marius Hills were analyzed. Spectral diversity was detected in visual evaluation of the spectra and was quantified using the MGM. The MGM-derived band positions are used to estimate the olivine's composition in a relative sense. Spectra of olivines from Moscoviense exhibit diversity in their absorption features, and this diversity suggests some variation in olivine Fe/Mg content. Olivines from Copernicus are observed to be spectrally homogeneous and thus are predicted to be more compositionally homogeneous than those at Moscoviense but are of broadly similar composition to the Moscoviense olivines. Olivines from Aristarchus and Marius exhibit clear spectral differences from those at Moscoviense and Copernicus but also exhibit features that suggest contributions from other phases. If the various precautions discussed here are weighed carefully, the methods presented here can be used to make general predictions of absolute olivine composition (Fe/Mg content). Copyright ?? 2011 by the American Geophysical Union.

  7. Olivine friction at the base of oceanic seismogenic zones

    USGS Publications Warehouse

    Boettcher, M.S.; Hirth, G.; Evans, B. M.

    2007-01-01

    We investigate the strength and frictional behavior of olivine aggregates at temperatures and effective confining pressures similar to those at the base of the seismogenic zone on a typical ridge transform fault. Triaxial compression tests were conducted on dry olivine powder (grain size ???60 ??m) at effective confining pressures between 50 and 300 MPa (using Argon as a pore fluid), temperatures between 600??C and 1000??C, and axial displacement rates from 0.06 to 60 ??m/s (axial strain rates from 3 ?? 10-6 to 3 ?? 10-3 s-1). Yielding shows a negative pressure dependence, consistent with predictions for shear enhanced compaction and with the observation that samples exhibit compaction during the initial stages of the experiments. A combination of mechanical data and microstructural observations demonstrate that deformation was accommodated by frictional processes. Sample strengths were pressure-dependent and nearly independent of temperature. Localized shear zones formed in initially homogeneous aggregates early in the experiments. The frictional response to changes in loading rate is well described by rate and state constitutive laws, with a transition from velocity-weakening to velocity-strengthening at 1000??C. Microstructural observations and physical models indicate that plastic yielding of asperities at high temperatures and low axial strain rates stabilizes frictional sliding. Extrapolation of our experimental data to geologic strain rates indicates that a transition from velocity weakening to velocity strengthening occurs at approximately 600??C, consistent with the focal depths of earthquakes in the oceanic lithosphere. Copyright 2007 by the American Geophysical Union.

  8. Shear Attenuation and Dispersion in Olivine + Orthopyroxene Aggregates (Synthetic Harzburgite)

    NASA Astrophysics Data System (ADS)

    Sundberg, M. I.; Cooper, R. F.

    2009-12-01

    Low-frequency (10-2.25olivine (ol) and orthopyroxene (opx). The attenuation spectra reveal “high-temperature background” behavior where attenuation diminishes smoothly and mildly with increasing frequency (QG-1~f -0.3). At higher frequencies (f >10-0.5 Hz), the attenuation spectra reveal the onset of an apparent peak, likely due to elastically-accommodated grain boundary sliding. Most importantly, these experiments reveal a strong dependence of attenuation on the modal abundance of opx for constant frequency, temperature, grain size, and melt fraction: attenuation increases by roughly a factor of two as the modal abundance of opx rises from 6 to 54 vol%. Further addition of opx leads to diminished attenuation. These reciprocating torsion measurements were complemented by a series of unidirectional microcreep tests, which demonstrate that the variation in attenuation is complemented by both a lower shear viscosity and a drop in the activation energy as opx mode increases. The behavior suggests that: (1) phase boundaries are potent absorbers of mechanical energy, and (2) the background attenuation in dry, melt-free upper mantle may be larger than that predicted from experimental studies conducted on single-phase olivine aggregates. The implications of these results for understanding seismic signatures of mid-ocean ridges and subduction zones are discussed.

  9. The x ray microprobe determination of chromium oxidation state in olivine from lunar basalt and kimberlitic diamonds

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    The synchrotron x-ray microprobe is being used to obtain oxidation state information on planetary materials with high spatial resolution. Initial results on chromium in olivine from various sources including laboratory experiments, lunar basalt, and kimberlitic diamonds are reported. The lunar olivine was dominated by Cr(2+) whereas the diamond inclusions had Cr(2+/Cr(3+) ratios up to about 0.3. The simpliest interpretation is that the terrestrial olivine crystallized in a more oxidizing environment than the lunar olivine.

  10. Olivine-gabbros and olivine-rich troctolites genesis through melt-rock reactions in oceanic spreading lithosphere: an experimental study up to 0.7 GPa

    NASA Astrophysics Data System (ADS)

    Francomme, Justine E.; Fumagalli, Patrizia; Borghini, Giulio

    2016-04-01

    Extensive melt-rock reaction and melt impregnation significantly affect not only the physical and chemical properties at mantle-crust transition, but also control the evolution of migrating melts. We performed reactive dissolution and crystallization experiments at pressure ≤ 0.7 GPa in a piston-cylinder apparatus to provide experimental constraints on genesis of olivine-rich troctolites and olivine-gabbros at mantle-crust transition in oceanic spreading lithosphere by melt-rock reaction. Our experiments are carried out by using Salt-Pyrex-Graphite-Magnesium assemblies and graphite-lined platinum capsules. Experimental charges are prepared with three layers: (1) basalt powder, (2) fine powder (1-10μm) of San Carlos olivine (Fo90.1), and (3) carbon spheres used as a melt trap. Three synthetic MORB-type melts have been used, two tholeiitic basalts (Mg#: 0.62, SiO2: 47.70 wt%, Na2O: 2.28 wt% and Mg#: 0.58, SiO2: 49.25 wt%, Na2O: 2.49 wt%) and a primitive one (Mg#: 0.74, SiO2: 48.25 wt%, Na2O: 1.80 wt%), in order to investigate the effect of melt composition. A rock/melt ratio of 0.7 has been kept fixed. Experiments have been conducted at temperatures from 1200 to 1300°C, at both step cooling and isothermal conditions for different run durations (from 12 to 72 hrs). They resulted in layered samples in which all the initial San Carlos olivine powder, analog of a dunitic pluton infiltrated by basaltic melt, is replaced by different lithologies from olivine-rich troctolite to olivine gabbro. In isothermal experiments, reacted melts have been successfully trapped in the carbon spheres allowing their chemical analysis; as expected the reacted melt has a higher Mg# than the initial one (e.g. from Mg#=0.62 to 0.73). Across the different lithologies Mg# of olivine is decreasing from the olivine-rich troctolite to the gabbro. Replacive olivine-rich troctolite has a poikilitic texture with rounded euhedral olivine and interstitial poikilitic plagioclase and clinopyroxene

  11. Calibrations of phase abundance, composition, and particle size distribution for olivine-orthopyroxene mixtures from reflectance spectra

    NASA Technical Reports Server (NTRS)

    Cloutis, Edward A.; Gaffey, Michael J.; Jackowski, Timothy L.; Reed, Kevin L.

    1986-01-01

    An analytical method for quantifying the characteristics (phase abundances, phase composition, and grain size) of an olivine-orthopyroxene mixture from reflectance spectra is described. The spectral parameters related to reflectance, wavelength position, and albedo are investigated; the absorption bands for the olivine-orthopyroxene mixture is also studied. Primary calibrations useful for the determination of the olivine-orthopyroxene mixture characteristics are examined.

  12. Martian Dunite NWA 2737: Petrographic Constraints on Geological History, Shock Events, and Olivine Color

    SciTech Connect

    Treiman,A.; Dyar, M.; McCanta, M.; Noble, S.; Pieters, C.

    2007-01-01

    Meteorite Northwest Africa (NWA) 2737 is the second known chassignite, an olivine-rich igneous rock with mineral compositions and isotopic ratios that suggest it formed on Mars. NWA 2737 consists of ?85% vol. olivine (Mg, molar Mg/(Mg + Fe), of 78.3 {+-} 0.4%), which is notable because it is black in hand sample and brown in thin section. Other minerals include chromite, pyroxenes (augite, pigeonite, orthopyroxene), and diaplectic glass of alkali-feldspar composition. Aqueous alteration is minimal and appears only as slight dissolution of glass. NWA 2737 formed by accumulation of olivine and chromite from a basaltic magma; the other minerals represent magma trapped among the cumulus grains. Minerals are compositionally homogeneous, consistent with chemical equilibration in late and postigneous cooling. Two-pyroxene thermometry gives equilibration temperatures 1150 C, implying a significant time spent at the basalt solidus. Olivine-spinel-pyroxene equilibria give ?825 C (possibly the T of mesostasis crystallization) at an oxidation state of QMF-1. This oxidation state is consistent with low Fe3+ in olivine (determined by EMP, Moessbauer spectra, and synchrotron micro-XANES spectroscopy) and with {approx}10% of the iron in pyroxene being Fe3+. NWA 2737 experienced two shock events. The first shock, to stage S5-S6, affected the olivine by producing in it planar deformation features, intense mosaicism and lattice strain, and abundant droplets of iron-nickel metal, 5-15 nm in diameter. At this stage the olivine became deeply colored, i.e., strongly absorbing at visible and near-infrared (NIR) wavelengths. This shock event and its thermal pulse probably occurred at {approx}170 Ma, the Ar-Ar age of NWA 2737. The colored olivine is cut by ribbons of coarser, uncolored olivine with long axes along [100] and shorter axes on {l_brace}021{r_brace} planes: These are consistent with the easy slip law for olivine [100]{l_brace}021{r_brace}, which is activated at moderate strain

  13. Oxygen isotopic composition of individual olivine grains from the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Weinbruch, S.; Zinner, E. K.; El Goresy, A.; Steele, I. M.; Palme, H.

    1993-01-01

    The oxygen isotopic composition of a variety of individual olivine grains (including refractory forsterite grains, cores of isolated olivine grains, FeO-rich rims, and individual matrix olivine grains) from the Allende CV3 meteorite was investigated by ion microprobe mass spectrometry, in order to obtain information on the formation mechanism of these samples. It was found that the most primitive (i.e., refractory) olivine in Allende is far less enriched in O-16 than are spinel and pyroxene in Ca,Al-rich inclusions, suggesting that Allende olivine must have formed in an environment that is less enriched in O-16 compared to the gas from which Ca,Al-inclusions are formed. FeO-rich (26-30 wt pct) rims of isolated olivine grains are significantly higher in delta-O-17 and delta-O-18 than forsteritic cores, suggesting that these rims formed by condensation from an oxidized gas with higher delta-O-17 than delta-O-18. Matrix olivine was found to be highest in FeO and to have the lowest enrichment in O-16.

  14. Experimental evidence for melt partitioning between olivine and orthopyroxene in partially molten harzburgite

    NASA Astrophysics Data System (ADS)

    Miller, Kevin J.; Zhu, Wen-lu; Montési, Laurent G. J.; Gaetani, Glenn A.; Le Roux, Véronique; Xiao, Xianghui

    2016-08-01

    Observations of dunite channels in ophiolites and uranium series disequilibria in mid-ocean ridge basalt suggest that melt transport in the upper mantle beneath mid-ocean ridges is strongly channelized. We present experimental evidence that spatial variations in mineralogy can also focus melt on the grain scale. This lithologic melt partitioning, which results from differences in the interfacial energies associated with olivine-melt and orthopyroxene-melt boundaries, may complement other melt focusing mechanisms in the upper mantle such as mechanical shear and pyroxene dissolution. We document here lithologic melt partitioning in olivine-/orthopyroxene-basaltic melt samples containing nominal olivine to orthopyroxene ratio of 3 to 2 and melt fractions of 0.02 to 0.20. Experimental samples were imaged using synchrotron-based X-ray microcomputed tomography at a resolution of 700 nm per voxel. By analyzing the local melt fraction distributions associated with olivine and orthopyroxene grains in each sample, we found that the melt partitioning coefficient, i.e., the ratio of melt fraction around olivine to that around orthopyroxene grains, varies between 1.1 and 1.6. The permeability and electrical conductivity of our digital samples were estimated using numerical models and compared to those of samples containing only olivine and basaltic melt. Our results suggest that lithologic melt partitioning and preferential localization of melt around olivine grains might play a role in melt focusing, potentially enhancing average melt ascent velocities.

  15. Oxygen isotopic composition of relict olivine grains in cosmic spherules: Links to chondrules from carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Rudraswami, N. G.; Prasad, M. Shyam; Nagashima, K.; Jones, R. H.

    2015-09-01

    Most olivine relict grains in cosmic spherules selected for the present study are pristine and have not been disturbed during their atmospheric entry, thereby preserving their chemical, mineralogical and isotopic compositions. In order to understand the origin of the particles, oxygen isotope compositions of relict olivine grains in twelve cosmic spherules collected from deep sea sediments of the Indian Ocean were studied using secondary ion mass spectrometry. Most of the data lie close to the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line, with Δ17O ranging from -5‰ to 0‰. The data overlap oxygen isotopic compositions of chondrules from carbonaceous chondrites such as CV, CK, CR and CM, which suggests that chondrules from carbonaceous chondrites are the source of relict grains in cosmic spherules. Chemical compositions of olivine in cosmic spherules are also very similar to chondrule olivine from carbonaceous chondrites. Several olivine relict grains in three cosmic spherules are 16O-rich (Δ17O -21.9‰ to -18.7‰), similar to oxygen isotopic compositions observed in calcium aluminum rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), and some porphyritic chondrules from carbonaceous chondrites. These grains appear to have recorded the initial oxygen isotopic composition of the inner solar nebula. Three olivine grains from two cosmic spherules have δ18O values >+20‰, which could be interpreted as mixing with stratospheric oxygen during atmospheric entry.

  16. Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

    NASA Technical Reports Server (NTRS)

    Usui, T.; Shearer, C. K.; Righter, K.; Jones, J. H.

    2011-01-01

    Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

  17. Detections and geologic context of local enrichments in olivine on Vesta with VIR/Dawn data

    NASA Astrophysics Data System (ADS)

    Ruesch, Ottaviano; Hiesinger, Harald; De Sanctis, Maria Cristina; Ammannito, Eleonora; Palomba, Ernesto; Longobardo, Andrea; Zambon, Francesca; Tosi, Federico; Capria, Maria Teresa; Capaccioni, Fabrizio; Frigeri, Alessandro; Fonte, Sergio; Magni, Gianfranco; Raymond, Carol A.; Russell, Christopher T.

    2014-09-01

    The magmatism characterizing the early history of the asteroid Vesta has long been investigated with the mafic and ultramafic meteorites howardite, eucrite, and diogenite (HED). The lack of geologic context for the meteorites, however, has limited its understanding. Here we use the visible to near-IR (VIR) orbital observations of Vesta's surface to detect relative enrichments in olivine and to study the associated geologic features. Because the near-IR signature of olivine on Vesta's surface is subtle relative to the widespread pyroxene absorption bands, a method was developed to distinguish olivine enrichments from admixture of pyroxenes with high Fe2+/M1, dark material, and potential Fe-bearing glass. Relative enrichment of olivine (~<50-60 vol %) is found in 2-5 km wide, morphologically fresh areas. Our global survey reveals a dozen of these areas clustering in the eastern hemisphere of Vesta. The hemispherical coincidence with a widespread, low enrichment in diogenite-like pyroxene suggests the presence of a distinct compositional terrain. On the central mound of the Rheasilvia impact basin, no olivine enrichment was found, suggesting the absence of an olivine-dominated mantle above the basin's excavation depth or, alternatively, a low amount of olivine homogeneously mixed with diogenite-like pyroxenes. Rare olivine-enriched areas in close proximity to diogenite-like pyroxene are found as part of material ejected by the Rheasilvia impact. Such cooccurrence is reminiscent of local, ultramafic lithologies within the crust. The possible formation of such lithologies on Vesta is supported by some HED meteorites dominated by olivine and orthopyroxene.

  18. H Diffusion in Olivine and Pyroxene from Peridotite Xenoliths and a Hawaiian Magma Speedometer

    NASA Technical Reports Server (NTRS)

    Peslier, A. H.; Bizimis, M.

    2014-01-01

    Hydrogen is present as a trace element in olivine and pyroxene and its content distribution in the mantle results from melting and metasomatic processes. Here we examine how these H contents can be disturbed during decompression. Hydrogen was analyzed by FTIR in olivine and pyroxene of spinel peridotite xenoliths from Salt Lake Crater (SLC) nephelinites which are part of the rejuvenated volcanism at Oahu (Hawaii) [1,2]. H mobility in pyroxene resulting from spinel exsolution during mantle upwelling Most pyroxenes in SLC peridotites exhibit exsolutions, characterized by spinel inclusions. Pyroxene edges where no exsolution are present have less H then their core near the spinel. Given that H does not enter spinel [3], subsolidus requilibration may have concentrated H in the pyroxene adjacent to the spinel exsolution during mantle upwelling. H diffusion in olivine during xenolith transport by its host magma and host magma ascent rates Olivines have lower water contents at the edge and near fractures compared to at their core, while the concentrations of all other chemical elements appear homogeneous. This suggests that some of the initial water has diffused out of the olivine. Water loss from the olivine is thought to occur during host-magma ascent and xenolith transport to the surface [4-6]. Diffusion modeling matches best the data when the initial water content used is that measured at the core of the olivines, implying that mantle water contents are preserved at the core of the olivines. The 3225 cm(sup -1) OH band at times varies independantly of other OH bands, suggesting uneven H distribution in olivine defects likely acquired during mantle metasomatism just prior to eruption and unequilibrated. Diffusion times (1-48 hrs) combined with depths of peridotite equilibration or of magma start of degassing allow to calculate ascent rates for the host nephelinite of 0.1 to 27 m/s.

  19. Magnetic properties of natural and synthetic olivines: high-field measurements

    NASA Astrophysics Data System (ADS)

    Ferre, E. C.; Martin-Hernandez, F.

    2004-12-01

    Olivine [(Fex, Mg1-x)2 SiO4] is an orthosilicate solid solution between fayalite [Fe2 SiO4] and forsterite [Mg2 SiO4]. Olivine is a major constituent of the Earth mantle that is abundant in oceanic and continental peridotites and mantle xenoliths. The magnetic properties of olivines have been previously investigated using gem quality natural crystals known as peridots (Zabargad) or using laboratory grown synthetic crystals. Magnetic investigations are generally performed using low magnetic field or neutron diffraction techniques. Optical microscopy and TEM imagery reveal that most olivine crystals host iron oxides formed by exsolution during cooling. Theoretically, the magnetic susceptibility of olivine should decrease linearly from fayalite to fayalite as a function of the Fe content. The magnetic behavior should range from antiferromagnetic at high Fe content, paramagnetic at intermediate Fe contents and diamagnetic at very low Fe contents. New magnetic measurements, performed on various high field instruments (vibrating sample magnetometer, torque magnetometer, cantilever magnetometer), both on natural and synthetic samples, display ferromagnetic behavior, interpreted as due to the systematic presence of titanomagnetite inclusions in olivine crystals. These results emphasize the need to conduct measurements in high field in order to isolate the intrinsic paramagnetic properties of olivines. These measurements demonstrate the orthorhombic nature of the intrinsic paramagnetic properties, but also yield new data concerning the relationship between crystallographic axes, magnetic anisotropy and other physical anisotropies: [100] = K1, [010] = K2 and [001] = K3. Preliminary results also indicate substantial variations in degree of paramagnetic anisotropy (P) and paramagnetic shape factor (T). For Fo92, P = 1.359 and T = -0.845. These intrinsic paramagnetic properties are used to model the magnetic behavior of olivine across a range of temperatures relevant to

  20. Minor and trace elements in olivines as probes into early igneous and mantle melting processes

    NASA Astrophysics Data System (ADS)

    Foley, Stephen F.; Prelevic, Dejan; Rehfeldt, Tatjana; Jacob, Dorrit E.

    2013-02-01

    The trace element composition of olivine is a rapidly growing research area that has several applications of great potential. Mantle olivines can be distinguished from volcanic olivines by lower concentrations of Ca (<700 ppm), Ti (<70 ppm), and often Cr. The melting of pyroxenites derived from recycled ocean crust can be recognized in volcanic olivines by correlations of Mn, Al, Sc and Co in addition to Ni. High Ni is characteristic of olivine derived from olivine-free source rocks, but alone it does not distinguish between recycling of ocean crust, continental crust, mantle wedge hybridization, and intra-mantle melt migration. Trace elements help to identify different types of non-peridotitic ultramafic rocks, including those not formed by ocean crust recycling. High Li may be caused by recycling of continental crust, as in Mediterranean post-collisional volcanics or by interaction with carbonatitic melts, and correlation with further elements such as Zn, Na, Ti and Ca will help to identify minerals in the source assemblages, such as phlogopite, spinel, garnet, amphiboles and carbonates, and thus the source of the olivine-free assemblages. Olivines often store the earliest chemical signals of melt loss in peridotites, but later absorb trace elements from passing melts, and are thus excellent monitors of the chemistry of metasomatic agents. Trace elements distinguish between Ti-enrichment by silicate melt metasomatism (high Ti, low Ca) and high-Ca signatures associated with plumes and rift regions that may be due to carbonate-silicate melts. Li may be enriched in olivine in the orogenic mantle, indicating the involvement of melted continental crustal material. Experimental data on element partitioning and diffusion currently partly conflicts with information from natural rocks.

  1. Cr, Mn, and Ca distributions for olivine in angritic systems: Constraints on the origins of Cr-rich and Ca-poor core olivine in angrite LEW87051

    NASA Technical Reports Server (NTRS)

    Mikouchi, T.; Mckay, G.; Le, L.

    1994-01-01

    Angrite meteorites are a type of basaltic achondrites that are noted for their very old cyrstallization ages (4.55 b.y.) and unusual chemical and mineralogical properties. In spite of great interest, only four angrites have been found. LEW87051 is the smallest one which weighs 0.6 g. It is a porphyritic rock with coarse subhedral to euhedral olivines set in a fine-grained groundmass which clearly represents a crystallized melt. The largest uncertainty about the petrogenesis of LEW87051 is the relationship between the large olivine crystals and the groundmass. Prinz et al. suggests that olivines are xenocrysts, while McKay et al. proposed a fractional cyrstallization model based on experimental studies. However, the crystals have Cr-rich and Ca-poor cores which do not match experimental olivines. Although Jurewicz and McKay tried to explaine the zoning of the rim by diffusion, some features are not explained. There also exists a definite composition boundary of Fe(2+) and MnO between the core and the rim. To clarify the origin of these olivines, we have performed experiments using LEW87051 analogs to measure the effects of oxygen fugacity on distribution coefficients of various elements in an angritic system.

  2. 3D Quantitative Confocal Laser Microscopy of Ilmenite Volume Distribution in Alpe Arami Olivine

    NASA Astrophysics Data System (ADS)

    Bozhilov, K. N.

    2001-12-01

    The deep origin of the Alpe Arami garnet lherzolite massif in the Swiss Alps proposed by Dobrzhinetskaya et al. (Science, 1996) has been a focus of heated debate. One of the lines of evidence supporting an exhumation from more than 200 km depth includes the abundance, distribution, and orientation of magnesian ilmenite rods in the oldest generation of olivine. This argument has been disputed in terms of the abundance of ilmenite and consequently the maximum TiO2 content in the discussed olivine. In order to address this issue, we have directly measured the volume fraction of ilmenite of the oldest generation of olivine by applying confocal laser scanning microscopy (CLSM). CLSM is a method which allows for three-dimensional imaging and quantitative volume determination by optical sectioning of the objects. The images for 3D reconstruction and measurements were acquired from petrographic thin sections in reflected laser light with 488 nm wavelength. Measurements of more than 80 olivine grains in six thin sections of our material yielded an average volume fraction of 0.31% ilmenite in the oldest generation of olivine from Alpe Arami. This translates into 0.23 wt.% TiO2 in olivine with error in determination of ±0.097 wt.%, a value significantly different from that of 0.02 to 0.03 wt.% TiO2 determined by Hacker et al. (Science, 1997) by a broad-beam microanalysis technique. During the complex geological history of the Alpe Arami massif, several events of metamorphism are recorded which all could have caused increased mobility of the mineral components. Evidence for loss of TiO2 from olivine is the tendency for high densities of ilmenite to be restricted to cores of old grains, the complete absence of ilmenite inclusions from the younger, recrystallized, generation of olivine, and reduction in ilmenite size and abundance in more serpentinized specimens. These observations suggest that only olivine grains with the highest concentrations of ilmenite are close to the

  3. Relict olivine, chondrule recycling, and the evolution of nebular oxygen reservoirs

    NASA Astrophysics Data System (ADS)

    Ruzicka, A.; Hiyagon, H.; Hutson, M.; Floss, C.

    2007-05-01

    Chondrules often contain relict olivine grains that did not crystallize in situ, providing opportunities to decipher how chondrule components evolved. We studied olivine in the Sahara-97210 (LL3.2), Wells (LL3.3) and Chainpur (LL3.4) chondrites using SEM, EMPA, and SIMS techniques. Oxygen isotopes were analyzed in 16 objects from all three meteorites, and trace elements were analyzed in Sahara-97210 and Chainpur. Two groups of olivine are identified based on oxygen isotope compositions. One group is enriched in 16O (Δ 17O ˜ - 8 to - 4‰) and falls close to the CCAM mixing line; it includes forsterite and Mg-rich olivine present as relict grains in Type II (ferrous) chondrules and the forsteritic cores of some isolated grains. These low-Δ 17O grains are poor in MnO (< 0.2 wt.%) and are usually enriched in CaO (˜ 0.3-0.65 wt.%). The other group is less enriched in 16O (Δ 17O ˜ - 3 to + 4 ‰); it includes normal (non-relict) ferrous olivine in type II chondrules, normal (non-relict) Mg-rich olivine in Type I (magnesian) chondrules, dusty olivine relict grains in Type I chondrules, and Mg-rich olivine relicts in a Type II and a Type I chondrule. These high-Δ 17O grains have variable CaO (0-0.95 wt.%) and MnO (˜ 0-0.45 wt.%) contents, with the more calcic and Mn-poor compositions associated with forsteritic olivine. Trace-element data show that forsteritic olivine grains in both oxygen groups are similarly enriched in refractory elements (Al, Sc, Y, Ca, Ti, V) and depleted in volatile elements (Cr, Mn, P, Rb, sometimes K and Na) compared to normal ferrous olivine, suggesting that variations in chemical composition reflect the extent of thermal processing (greater for magnesian olivine). The data are consistent with a model in which nebular reservoirs became less enriched in 16O with time. An earlier episode of chondrule formation produced Type I chondrules and isolated forsterites in carbonaceous chondrites, and forsteritic grains that were incorporated into

  4. Fayalitic Olivine in Matrix of the Krymka LL3.1 Chondrite

    NASA Astrophysics Data System (ADS)

    Weisberg, M. K.; Zolensky, M. E.; Prinz, M.

    1995-09-01

    INTRODUCTION. Matrix persists as one of the most poorly characterized chondritic components. Its aggregational nature makes it an excellent place to search for primitive chondritic components that prevailed in the nebula during and after chondrule formation as well as components recording processes that predated and postdated accretion. In this study we focus on the occurrence and formation of the fayalitic olivine in the matrix of the Krymka LL3.1 unequilibrated ordinary chondrite. RESULTS. We limited our study to matrix areas clearly sandwiched between chondrules and did not include chondrule rims. In Krymka, matrix is coarser-grained and more Fe-rich than the rim material. Matrix is also highly variable in the size, shape and composition of its components, whereas chondrule rims appear more uniform. Krymka matrix is an aggregation of diverse mineral and lithic components. Mineral components include olivine, enstatite, diopsidic pyroxene, Ti-Al-rich Ca-pyroxene, hedenbergite, amorphous silicate material, spinel, oxides, troilite, and metal. Olivine is clearly dominant (~75% normative) and occurs in a variety of textures and compositions. Fayalitic olivine (Fa(sub)(58-94), avg.=Fa(sub)(72)) is ubiquitous throughout the matrix and occurs as (1) Isolated platelets (typically 1-3 micrometers x 3-5 micrometers, with some up to 10 micrometers in length), (2) Platelet clusters, which include randomly oriented platelets and/or intergrown platelets, (3) Platelet overgrowths which are overgrowths of parallel platelets on surfaces of larger (10-300 micrometers), more magnesian (Fa(sub)(4-34), avg.=Fa(sub)(19)) olivine fragments, (4) Euhedral-subhedral crystals (1-10 micrometers) which are often associated with and compositionally similar to platelets, and (5) Fluffy aggregates - irregularly shaped porous aggregates of submicron crystals. TEM study of the overgrowths reveals that the direction of elongation of the fayalitic platelets is along the c axis corresponding with

  5. First Row Transition Metals in Olivine - Petrogenetic Tracers for the Evolution of Mantle-Derived Magmas

    NASA Astrophysics Data System (ADS)

    Locmelis, M.; Arevalo, R. D., Jr.; Puchtel, I. S.; Barnes, S. J.; Fiorentini, M. L.

    2015-12-01

    Olivine is the most abundant mineral in the upper mantle and a major constituent of most mantle-derived rocks. However, despite its abundance, studies on the trace element chemistry of olivine are underrepresented in the literature. We present the results of a comprehensive study on the contents of first-row transition metals (FRTM: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn), Ga and Ge in olivines from 2.7-3.5 Ga old Munro- and Barberton-type komatiites from the Kapvaal and Zimbabwe Cratons in southern Africa, the Yilgarn Craton in Australia, and the Superior Craton in Canada. Komatiitic olivines are compared to olivines from a Devonian-Carboniferous mantle peridotite (Finero, Italy) and contemporary ocean Island basalts (OIB, from St. Helena, South Atlantic Ocean). The olivine major element chemistry was determined using a JEOL JXA-8900 Superprobe at the University of Maryland. Trace element contents were determined using a Photon Machines Analyte G2 193 nm Excimer laser ablation system coupled to a Nu Instruments AttoM single collector ICP-MS at NASA Goddard Space Flight Center. Medium resolution mass discrimination (m/Δm = 2500, at 5% peak intensity) was leveraged to separate isobaric interferences and support accurate quantitation of elemental abundances. The results show that olivines from komatiites are largely depleted in FRTM, Ga and Ge relative to the composition of the primitive mantle (FRTMPM-norm = ~0.01 - 1). All komatiitic olivines have similar mantle-normalized trace element patterns, regardless of age and/or locality. Olivines from the Finero mantle peridotite and the St. Helena OIB are similarly depleted. However, compared to komatiites, grains from Finero are enriched in Ge and distinctly depleted in Ti, V, Cr, and Ga, whereas olivines from St. Helena have overall flatter normalized trace element patterns. The distinct patterns show that olivine chemistry can be used to identify and understand the source and evolution of mantle-derived rocks

  6. Fe-Mg-Mn relations of ureilite olivines and pyroxenes and the genesis of ureilites

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, D. W.

    1986-01-01

    Microprobe analyses of ureilite and pigeonite cores are studied. The Fe/Mn-Fe/Mg relationship in the olivine core is examined. It is observed that magnetic processs such as fractional crystallization and partial melting, and FeO reduction contribute to the olivine core composition. The study of the Mg/Mn and Fe/Mn distributions reveals that these two distributions are not in equilibrium in the olivine and pigeonite cores. The effect of a reducing agent, carbon, on the ureilite genesis is investigated. It is concluded that fractional crystallization and FeO reduction are the major processes of ureilite genesis.

  7. Multi-stage kimberlite evolution tracked in zoned olivine from the Benfontein sill, South Africa

    NASA Astrophysics Data System (ADS)

    Howarth, Geoffrey H.; Taylor, Lawrence A.

    2016-10-01

    Olivine is the dominant mineral present in kimberlite magmas; however, due to the volatile-rich nature of most kimberlites, they rarely survive late-stage serpentinisation. Here we present major and trace element data for a rare example of ultra-fresh olivine in a macrocrystic calcite kimberlite from the Benfontein kimberlite sill complex. Olivines are characterised by xenocrystic cores surrounded by multiple growth zones representing melt crystallisation and late-stage equilibration. Two distinct core populations are distinguished: Type 1) low Fo (88-89), Ni-rich, Ca- and Na-rich cores, interpreted here to be the result of carbonate-silicate metasomatism potentially as part of the earliest stages of kimberlite magmatism, and Type 2) high Fo (91-93), Ni-rich, low-Ca cores derived from a typical garnet peridotite mantle source. In both cases, the cores have transitional margins (Fo89-90) representing equilibration with a proto-kimberlite melt. Trace element concentrations, in particular Cr, of these transition zones suggest formation of the proto-kimberlite melt through assimilation of orthopyroxene from the surrounding garnet peridotite lithology. Trace element trends in the surrounding melt-zone olivine (Fo87-90) suggest evolution of the kimberlite through progressive olivine crystallisation. The final stages of olivine growth are represented by Fe-rich (Fo85) and P-rich olivine indicating kimberlite evolution to mafic compositions. Fine (< 60 μm), Mg-rich olivine rims (Fo94-98) represent equilibration with the final stages of kimberlite evolution back to Fe-poor carbonatitic melts. We present a step-by-step model for kimberlite magma genesis and evolution from mantle to crust tracked by the chemistry of olivines in the Benfontein kimberlite. These steps include early stages of metasomatism and mantle assimilation followed by direct crystallisation of the kimberlite melt and late-stage equilibration with the evolved carbonatitic residual liquids. The Ca contents

  8. Trace Elements in Olivine in Italian Potassic Volcanic Rocks Distinguish Between Mantle Metasomatism by Carbonatitic and Silicate Melts

    NASA Astrophysics Data System (ADS)

    Foley, S. F.; Ammannati, E.; Jacob, D. E.; Avanzinelli, R.; Conticelli, S.

    2014-12-01

    The Italian Peninsula is the site of intense subduction-related potassic magmatism with bimodal character in terms of silica activity: Ca-poor silica-saturated lamproitic rocks and Ca-enriched silica-undersaturated leucitites. Lamproitic magmas formed in the early phases of magmatic activity and were followed by leucititic magmas. The primary magmas are generated in the sub-continental lithospheric mantle at the destructive plate margin, and both series have olivine as the first crystallizing phenocrysts. Trace elements in olivine phenocrysts are important in recognizing metasomatic effects on the mineralogy of the mantle source. Since Ni is the most compatible trace element in olivine, particularly in alkaline melts, modal changes of olivine in the source strongly affect its bulk partition coefficient, and therefore its content in primary melts and in olivine that crystallizes from them.The concentration of other compatible trace elements (e.g. Mn, Co) in olivine phenocrysts also depends on the abundance of olivine in the magma source. Ni contents in olivine of the Italian rocks show a clear bimodal distribution. Olivine from lamproitic samples has systematically higher Fo and Ni contents, whereas olivine from leucititic rocks never exceeds Fo92 and has markedly lower Ni, reaching among the lowest levels ever observed in olivine phenocrysts in primitive melts. The Mn/Fe ratio of olivine is also sensitive to changes of the modal abundance of olivine in the source, 100*Mn/Fe of olivine from lamproitic rocks never exceeds 2, while it is always >1.8 in leucititic rocks, meaning that the leucitite source regions are much richer in olivine. Lithium is generally enriched in the crust and in sediments compared to the lithospheric mantle and to mantle-derived melts,so that Li in olivine above 10 ppm is suggested to indicate recycled sediments. Li contents are up to 35 ppm in leucititic olivines and up to >50 ppm in lamproitic olivines, confirming the recycling of crustal

  9. Metastable olivine wedge beneath northeast China and its applications

    NASA Astrophysics Data System (ADS)

    Jiang, G.; Zhao, D.; Zhang, G.

    2013-12-01

    When the Pacific slab subducted into the mantle transition zone, there might exist a metastable olivine wedge (MOW) inside the slab due to the phase transition. Lots of researchers have adopted such various methods to detect the characteristics of this MOW as the forward modeling of travel times, shear wave amplitude patterns, teleseismic P wave coda, receiver function imaging, thermodynamic simulation and so on. Almost all results could be more or less affected by the source, the receiver and/or the velocity model passed through by the seismic rays. In this study, we have used 21 deep earthquakes, greater than 400 km and locating beneath northeast China, to study the velocity within the MOW. For more precisions, we have done further modifications in two ways based on our previous studies. (1) Double-difference location method is used to relocate all events with an error of 1-2 km with the data recorded by stations both at northeast China and at Japan. All relocated events locate in a zone about 30 km away from the upper boundary of Pacific slab. (2) Double residual travel times, generated by an event-pair at a common station at only Japan, are used to constrain the velocity anomaly rather than the residuals themselves. As a result, we have found that an ultra-lower velocity zone (ULVZ), averagely -7% relative to the iasp91 model, exists within the subducted Pacific slab around the deep earthquakes, which might be represented as the metastable olivine wedge. Because of the lower-velocity corresponding to the lower-density, the MOW would provide upward buoyancy forces which might prevent the slab from free subduction into the mantle transition zone. This feed-back mechanism of MOW to the slab is called ';parachute-effect', which is characterized by other researchers. In addition, the existence of the ULVZ or the MOW in the slab may supply a possible mechanism for triggering deep earthquakes, called ';phase transformation faulting', which was already proposed few

  10. The elastic constants of San Carlos olivine to 17 GPa

    SciTech Connect

    Abramson, E.H.; Brown, J.M.; Slutsky, L.J.; Zaug, J.

    1997-06-01

    All elastic constants, the average bulk and shear moduli, and the lattice parameters of San Carlos olivine (Fo{sub 90}) (initial density 3.355gm/cm{sup 3}) have been determined to a pressure of 12 GPa at room temperature. Measurements of c{sub 11}, c{sub 33}, c{sub 13}, and c{sub 55} have been extended to 17 GPa. The pressure dependence of the adiabatic, isotropic (Hashin-Shtrikman bounds) bulk modulus, and shear modulus may be expressed as K{sub HS}=129.4+4.29P and by G{sub HS}=78+1.71P{minus}0.027P{sup 2}, where both the pressure and the moduli are in gigapascals. The isothermal compression of olivine is described by a bulk modulus given as K{sub T}=126.3+4.28P. Elastic constants other than c{sub 55} can be adequately represented by a linear relationship in pressure. In the order (c{sub 11},c{sub 12},c{sub 13},c{sub 22},c{sub 23},c{sub 33},c{sub 44},c{sub 55},c{sub 66}) the 1 bar intercepts (gigapascal units) are (320.5, 68.1, 71.6, 196.5, 76.8, 233.5, 64.0, 77.0, 78.7). The first derivatives are (6.54, 3.86, 3.57, 5.38, 3.37, 5.51, 1.67, 1.81, 1.93). The second derivative for c{sub 55} is {minus}0.070GPa{sup {minus}1}. Incompressibilities for the three axes may also be expressed as linear relationships with pressure. In the order of {bold a, b}, and {bold c} axes the intercepts in gigapascals are (547.8, 285.8, 381.8) and the first derivatives are (20.1, 12.3, 14.0).{copyright} 1997 American Geophysical Union

  11. Reactive flow as dominant evolution process in the lowermost oceanic crust: evidence from olivine of the Pineto ophiolite (Corsica)

    NASA Astrophysics Data System (ADS)

    Sanfilippo, Alessio; Tribuzio, Riccardo; Tiepolo, Massimo; Berno, Davide

    2015-10-01

    The Jurassic Pineto ophiolite from Corsica exposes a ~1-km-thick troctolite-olivine-gabbro sequence, interpreted to represent a lowermost sector of the gabbroic oceanic crust from a (ultra-)slow spreading system. To constrain the petrogenesis of the olivine-gabbros, minor and trace element analyses of olivine (forsterite = 84-82 mol%) were carried out. Olivine from the olivine-gabbros is depleted in incompatible trace elements (Sc, V, Ti, Y, Zr and heavy rare earth elements) with respect to olivines from associated troctolites. Depleted incompatible element compositions are also shown by olivine (forsterite = 86 mol%) from a clinopyroxene-rich troctolite. The incompatible element compositions of olivine argue against a petrogenetic process entirely driven by fractional crystallization. We propose that melts migrating through an olivine-plagioclase crystal mush chemically evolved by reaction with the existing minerals, changing in composition as it flowed upward. The melt residual from these interactions led to partial dissolution of preexisting olivine and to crystallization of clinopyroxene, generating olivine-gabbro bodies within a troctolite matrix. Reactive flow was the major evolution process active in the ~1-km crustal transect exposed at the Pineto ophiolite, producing lithological variations classically attributed to fractional crystallization processes.

  12. Trace element composition of olivine - implications for the evolution of the olivine gabbro-troctolite-hosted Voisey's Bay Ni-Cu-Co sulfide deposit, Labrador

    NASA Astrophysics Data System (ADS)

    Bulle, F.; Layne, G. D.

    2011-12-01

    The Mesoproterozoic Voisey's Bay intrusion is part of the Nain Plutonic Suite, which transects the 1.85 Ga collisional boundary between the Proterozoic Churchill Province and the Archean Nain Province in Eastern Labrador. The intrusion comprises a group of troctolitic to olivine gabbroic bodies linked by olivine gabbro dikes; together these rocks host the world-class Voisey's Bay Ni-Cu-Co sulfide deposit. Zones of massive and disseminated sulfide mineralization (Reid Brook, Discovery Hill, Mini-Ovoid and Ovoid) occur within a dike and at the entry line of this dike into a larger intrusion termed the Eastern Deeps [1, 2, 3]. At least two pulses of magma have generated the intrusion and the associated sulfide mineralization; an initial surge that achieved sulfide saturation by interacting with upper crustal rocks, and a later pulse of fresh, undepleted magma that forced the initial magma upwards and both remobilized the immiscible sulfide liquid and upgraded it in metal content [1, 2, 3]. Previous research [1, 2] has shown that the Ni content of olivine from the distinct sulfide-bearing host rocks is highly variable, and also indicative of both magma mixing and interaction of silicate magmas with sulfide. To further validate the significance of the olivine chemistry as a tracer for ore-forming petrological processes, we have determined the abundances of Cr, Mn, Co, Ni, Zn in olivines from the various mafic lithologies of the Eastern Deeps intrusion using Secondary Ion Mass Spectrometry. We present systematic variations in Mn, Co, Ni and Zn with Fo-content in olivines for both sulfide-free and sulfide-bearing zones. Olivines from mineralized and brecciated troctolitic/gabbroic zones display significantly higher Mn (up to 11,000 ppm) and Zn (up to 550 ppm) concentrations than those from nominally barren counterparts. The barren troctolite, broadly termed normal troctolite (NT), is a petrographically homogenous plagioclase and olivine cumulate. However, olivine

  13. Reinvestigation of the olivine-spinel transformation in Ni2SiO4 and the incongruent melting of Ni2SiO4 olivine

    NASA Technical Reports Server (NTRS)

    Ma, C.-B.

    1974-01-01

    The olivine-spinel transformation and the melting behavior of Ni2SiO4 were investigated over the PT ranges of 20-40 kbar, 650-1200 C, and 5-13 kbar, 1600-1700 C, respectively. It was confirmed that Ni2SiO4 olivine melts incongruently at high pressures and that it is a stable phase until melting occurs. The PT slope of the incongruent melting curve is approximately 105 bars/deg. The olivine-spinel transformation curve was shown to be a reversible univariant curve, and could be expressed by the linear equation P(bars) equals 23,300 + 11.8 x T(deg C). The transformation curve determined by Akimoto et al. (1965) is nearly parallel to that of the present work, but lies at pressures about 12% lower.

  14. Charge Localization and Transport in Lithiated Olivine Phosphate Materials

    SciTech Connect

    Yu, Jianguo; Rosso, Kevin M.; Liu, Jun

    2011-11-10

    We report density functional theory (DFT) calculations for olivine-type LiTMPO4 and TMPO4 (TM=Mn, Fe, Co, Ni) structures, using GGA+U and the B3LYP hybrid density functional that includes nonlocal Fock exchange. TM is typically characterized in terms of the formal oxide states of 2+ or 3+, corresponding to TM with localized charge in LiTMPO4 and TMPO4 structures, respectively, in which electron transport would take place by thermally activated hopping of electrons strongly localized on the transition metal (small polarons). In this work, we assess the validity of the concept of formal TM oxidation states in these materials, and conclude that the valence depends in large part on the strength of d-p hybridization. Stable small polaron formation, i.e., mixed 2+ and 3+ valence states, appears to require that the ratio of differences in the metal and oxygen ionic charges (dQTM/dQO) of the two end member phases is larger than 2, corresponding to the mixed-valence TM system. If the ratio of dQTM/dQO is smaller than 2, excess electrons prefer delocalization and the system behaves more single-valence like with charge transport more akin to metallic conduction. The critical ratio emerging from our analysis may turn out to be relevant to other transition metal systems as well, as a criterion to discriminate single-valence or mixed-valence characteristics and hence the predominant conduction mechanism.

  15. Water in Pyroxene and Olivine from Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Peslier, A. H.

    2012-01-01

    Water in the interior of terrestrial planets can be dissolved in fluids or melts and hydrous phases, but can also be locked as protons attached to structural oxygen in lattice defects in nominally anhydrous minerals (NAM) like olivine, pyroxene, or feldspar [1-3]. Although these minerals contain only tens to hundreds of ppm H2O, this water can amount to at least one ocean in mass when added at planetary scales because of the modal dominance of NAM in the mantle and crust [4]. Moreover these trace amounts of water can have drastic effects on melting temperature, rheology, electrical and heat conductivity, and seismic wave attenuation [5]. There is presently a debate on how much water is present in the martian mantle. Secondary ionization mass spectrometry (SIMS) studies of NAM [6], amphiboles and glass in melt inclusions [7-10], and apatites [11, 12] from Martian meteorites report finding as much water as in the same phases from Earth's igneous rocks. Most martian hydrous minerals, however, generally have the relevant sites filled with Cl and F instead of H [13, 14], and experiments using Cl [15] in parent melts can reproduce Martian basalt compositions as well as those with water [16]. We are in the process of analyzing Martian meteorite minerals by Fourier transform infrared spectrometry (FTIR) in order to constrain the role of water in this planet s formation and magmatic evolution

  16. An Interactive Computer Program for Simulating the Effects of Olivine Fractionation from Basaltic and Ultrabasic Liquids.

    ERIC Educational Resources Information Center

    Pearce, Thomas H.

    1983-01-01

    Describes interactive computer program (listing available from author) which simulates olivine fractionation from basaltic/ultrabasic liquid. The menu-driven nature of the program (for Apple II microcomputer) allows students to select ideal Rayleigh fractionation or equilibrium crystallization. (JN)

  17. Olivine-Orthopyroxene Equilibrium in Metal-rich Systems: Applications to Achondrites and Equilibrated Chondrites

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Benedix, G. K.; McCoy, T. J.

    2003-01-01

    Olivine and orthopyroxene are major minerals in every type of stony meteorite. The majority of achondritic meteorites and silicate-bearing iron meteorites have experienced high temperatures. If these temperatures persisted for an extended period of time then the iron contents of olivine and orthopyroxene should be in equilibrium. In their study of ungrouped clasts and chondritic meteorites, suggested that the equilibrium compositions of olivine and orthopyroxene should fall on a mixing line between LL chondrites and aubrites. Here we show that this is not necessarily the case and that a range of FeO contents in olivine and orthopyroxene can be in equilibrium with each other. The key parameters that determine the equilibrium Fe content in these minerals are temperature, oxygen fugacity (fO2), and silica activity (aSiO2).

  18. Co-Formation of Ringwoodite, Wadsleyite, and Olivine in Shock Veins

    NASA Astrophysics Data System (ADS)

    Pittarello, L.; Ji, G.; Yamaguchi, A.; Schryvers, D.; Debaille, V.; Claeys, Ph.

    2016-08-01

    High-pressure polymorphs of olivine occur in shock veins in a L6 meteorite. TEM studies and petrologic assumptions have allowed a possible interpretation of the formation process, which also explains the change in Mg# between coexisting phases.

  19. Metastable olivine provides regional constraints on hydrogen content based on transformation kinetics

    NASA Astrophysics Data System (ADS)

    Du Frane, W. L.; Sharp, T. G.; Mosenfelder, J. L.; Leinenweber, K. D.

    2009-12-01

    The existence of metastable olivine has been debated as a possible trigger of deep focus earthquakes. Of equal importance, its existence may constrain the amount of hydrogen being subducted into the Earth’s transition zone. Olivine transformation rates into wadsleyite and ringwoodite have been demonstrated to be dependent on hydrogen content, and determine whether metastable olivine persists into the Earth’s mantle transition zone as downwelling material. For nominally anhydrous olivine, in this and previous studies, transformation rates decrease over time as a rigid reaction rim is formed. If viscoelastic relaxation of the rim occurs at a relatively slow rate, strain energy resulting from the negative volume change of the reaction counteracts the chemical free energy driving force for growth. It has been proposed that hydrogen enhances olivine transformation rates through hydrolytic weakening of the growth rim, which promotes relaxation of transformation stress, but it is not clear how much hydrogen is required for this mechanism to occur. We present ringwoodite growth rate measurements for interface-controlled growth, using olivine spheres hydrated in a piston cylinder with 75 +/- 15 ppm H2O and nominally anhydrous San Carlos olivine spheres with ≤ 10 ppm H2O. Hydrogen contents have been determined using new FTIR and SIMS data that indicate that hydrogen partitions into the growth rim as it forms. As the rim continues to grow and the core becomes depleted, the rim will eventually exhaust itself of hydrogen and may later become rigid if there is not enough hydrogen available to weaken the growth rim throughout transformation. However, we did not see evidence of non-linear rim growth in samples with 75 ppm H2O, with up to 76% growth fraction at 1100 °C. For olivine initially containing 75 ppm H2O, the ringwoodite growth rates at 18 GPa are 5.1(+/-0.4)x10-11 at 700 °C, 1.8(+/- 0.6)x10-9 m/s at 900 °C, 3.8(+/-1.5)x10-8 at 1100 °C with activation enthalpy of

  20. Optical absorption and radiative heat transport in olivine at high temperature

    NASA Technical Reports Server (NTRS)

    Shankland, T. J.; Nitsan, U.; Duba, A. G.

    1979-01-01

    Results are presented of measurements of the optical absorption spectra (300-8000 nm) of olivine as a function of temperature (300-1700 K) under conditions of controlled and known oxygen fugacity within the stability field of the samples. The absorption spectra are used to calculate the temperature-dependent radiative transfer coefficient of olivine and to numerically study the accuracy of the method. The present absorption measurements in olivine under oxidizing conditions known to be within the olivine stability field indicate that the effective radiative conductivity K(R) is lower than that obtained in previous studies under different experimental conditions. The lower value of K(R) makes it more likely that some of the earth's internal heat is removed by convection and less likely that thermal models involving conduction and radiation alone will satisfactorily explain thermal conditions in the earth's mantle.

  1. Calculated diffusion coefficients and the growth rate of olivine in a basalt magma

    NASA Technical Reports Server (NTRS)

    Donaldson, C. H.

    1975-01-01

    Concentration gradients in glass adjacent to skeletal olivines in a basalt have been examined by electron probe. The glass is depleted in Mg, Fe, and Cr and enriched in Si, Al, Na, and Ca relative to that far from olivine. Ionic diffusion coefficients for the glass compositions are calculated from temperature, ionic radius and melt viscosity, using the Stokes-Einstein relation. At 1170 C, the diffusion coefficient of Mg(2+) ions in the basalt is 4.5 billionths sq cm per sec. Comparison with measured diffusion coefficients in a mugearite suggests this value may be 16 times too small. The concentration gradient data and the diffusion coefficients are used to calculate instantaneous olivine growth rates. Growth necessarily preceded emplacement such that the composition of the crystals plus the enclosing glass need not be that of a melt. The computed olivine growth rates are compatible with the rate of crystallization deduced for the Skaegaard intrusion.

  2. Olivine Microstructures in the Miller Range 99301 (LL6) Ordinary Chondrite

    NASA Astrophysics Data System (ADS)

    Hutson, M. L.; Hugo, R.; Ruzicka, A. M.; Rubin, A. E.

    2009-03-01

    We used Transmission Electron Microscope (TEM) imaging to examine microstructures in MIL 99301 (LL6) olivine grains in order to understand more fully this meteorite’s deformation and thermal history.

  3. Implications of Heterogeneous Sr-Isotopes in Olivines from Samoan Lavas

    NASA Astrophysics Data System (ADS)

    Reinhard, A.; Jackson, M. G.; Harvey, J.

    2015-12-01

    In Ocean Island Basalts (OIB), relationships between helium isotopes and heavy radiogenic isotopes, like 87Sr/86Sr, are often used to constrain the evolution of the mantle. In OIB, 87Sr/86Sr is often measured on whole rock powders, while 3He/4He is measured in olivine hosted melt inclusions. Comparing these values is robust so long as both reservoirs have the same 87Sr/86Sr. However, new evidence suggests significant 87Sr/86Sr disequilibrium can exist between OIB whole rocks and the olivines they host. The data presented show 87Sr/86Sr can vary by ~2000 ppm between the whole rock (0.7089) and olivine hosted melt inclusions (0.7075) in fresh, zero-age Samoan basalts. Additionally, samples with the highest whole rock 87Sr/86Sr also show the greatest disequilibrium between whole rocks and olivines. Importantly, Sr is highly incompatible in the olivine lattice, thus melt inclusions host nearly all Sr in olivines; measuring pooled olivines provides an average 87Sr/86Sr for the melt inclusion population. The origin of whole rock- olivine 87Sr/86Sr disequilibrium is not well understood. The assimilation of seawater derived components could produce this effect, but is inconsistent with Cl/K data collected on submarine glasses. Whole rock 87Sr/86Sr increases with silica content suggesting 87Sr/86Sr disequilibrium is the result of mixing magmas derived from heterogeneous mantle sources. If olivine crystalizes from a low 87Sr/86Sr reservoir, and later mixes with a higher 87Sr/ 86Sr magma, the signature of the initial magma would be captured in the melt inclusions. This whole rock- olivine 87Sr/86Sr disequilibrium has the potential to revolutionize our understanding of the relationships between 3He/4He and 87Sr/86Sr in OIB. These relationships are central to chemical geodynamic models, and establishing a new method for measuring both He and Sr isotopes in olivine hosted melt inclusions will provide new frontiers for future research exploring the noble gas evolution of the

  4. A new olivine-melt thermometer/hygrometer based on Ni partitioning

    NASA Astrophysics Data System (ADS)

    Pu, X.; Lange, R. A.; Moore, G. M.

    2015-12-01

    Temperature and H2O content are key to understanding the origin and evolution of arc basalts. Here we propose that the strong temperature dependence on DNi (olivine-melt), quantified by Li & Ripley (2010), can be used as a thermometer that is largely independent of melt H2O concentration. Currently, the most widely used olivine-melt thermometers (based on partitioning of Mg) are strongly dependent on melt H2O content, and application to hydrous basalts requires that melt H2O contents already be known. If an H2O-independent olivine-melt thermometer could be developed, then application to hydrous basalts will lead to accurate temperatures at the time of olivine crystallization. These temperatures can then be combined with Mg-based olivine-melt thermometers to obtain the magnitude of ∆T, the depression of the olivine liquidus due to melt H2O concentration. In turn, hydrous phase equilibrium data from the literature allow melt H2O concentration to be derived from ∆T (e.g., Medard &Grove, 2008; Almeev et al., 2007). Thus, an H2O-independent olivine-melt thermometer can be used to calculate melt H2O concentrations at the onset of olivine crystallization. To test this approach in hydrous systems, we obtained new Ni concentration data for the H2O-saturated basaltic andesite phase equilibrium experiments of Moore and Carmichael (1998). The predicted temperatures from the inverted L&R'10 model are within 25° C of the measured experimental temperatures. This approach was also tested on 192 olivine-liquid pairs from 18 experimental studies that reported Ni content in both olivine and melt. The average residuals between the calculated and experimental T is -16 °C. We also calibrated a new model based on the same format above, but with an additional pressure term (average residual of -2 °C). Application of this approach to lavas for which H2O in olivine-hosted melt inclusions have been analyzed in the literature shows excellent agreement.

  5. Effect of metamorphism on isolated olivine grains in CO3 chondrites

    NASA Technical Reports Server (NTRS)

    Jones, Rhian H.

    1993-01-01

    The presence of a metamorphic sequence in the CO3 chondrite group has been shown previously to result in changes in properties of chondrule silicates. However, the role of isolated olivine grains during metamorphism of these chondrites has not been addressed. Isolated olivine grains in two metamorphosed CO3 chondrites, Lance and Isna, have been investigated in this study in order to assess the compositional properties of isolated olivine grains that may be attributable to metamorphism. Compositional changes in isolated olivines with increasing petrologic subtype are very similar to changes in chondrule olivines in the same chondrites. Olivine compositions from all occurrences (chondrules, isolated grains, and matrix) converge with increasing petrologic subtype. The degree of equilibration of minor elements is qualitatively related to the diffusion rate of each element in olivine, suggesting that diffusion-controlled processes are the most important processes responsible for compositional changes within the metamorphic sequence. The data are consistent with metamorphism taking place in a closed system on the CO3 chondrite parent body. Fe-poor olivine grains in metamorphosed chondrites are characterized by an Fe-rich rim, which is the result of diffusion of Fe into the grains from Fe-rich matrix. In some instances, 'complex', Fe-rich rims have been identified, which appear to have originated as igneous overgrowths and subsequently to have been overprinted by diffusion processes during metamorphism. Processes experienced by CO3 chondrites are more similar to those experienced by the ordinary chondrites than to those encountered by other carbonaceous chondrites, such as the CV3 group.

  6. Dusting the Ocean with Olivine: An Effective Method for Climate Engineering?

    NASA Astrophysics Data System (ADS)

    Sendel, J.

    2015-12-01

    As a preliminary experiment, a low-cost method to determine the capacity of water to take up carbon dioxide was used. Several factors affecting the solubility of CO2 in water were tested. Among the factors tested was the presence of olivine, a mineral used to enhance the uptake of CO2 by soils through a process called Enhanced Weathering. Literature search indicated that olivine increases the alkalinity and concentration of silicate in water and thus increasing the capacity of water to take up CO2. This, however, could not be verified with the said method. Albeit, further experiments showed that the concentration of silicate in distilled water with olivine increases if the water was acidified with CO2. In an additional investigation, to different types of water (distilled water, Baltic seawater (15 ppt) and North Atlantic Seawater (35 ppt)), powdered olivine was added in a concentration of 1g/litre. These were treated with different concentrations of CO2 (400,800,1200 ppm) at 15°C. 400 ppm is the present concentration of CO2 in the atmosphere. Alkalinity, pH, silicate and magnesium concentrations were monitored for a period of 10 days. To test if the silicate released from the dissolution of olivine promotes the growth of phytoplankton, the diatom, Phaeodactylum tricornutum, was cultured in the Baltic seawater used for the above experiments and Chlorophyll a concentrations were measured. First results show that the effectiveness of olivine in increasing the alkalinity, pH, silicate and magnesium concentrations is limited only in the distilled water sample. This may be due to other ions in seawater which might be interfering in the dissolution of olivine. The powdered olivine sank immediately to the bottom of the containers, indicating that this does not stay long in the water column to cause any significant changes in CO2 uptake, which occurs primarily in the surface of the ocean.

  7. Oxygen isotopic constraints on the origin of Mg-rich olivines from chondritic meteorites

    NASA Astrophysics Data System (ADS)

    Libourel, Guy; Chaussidon, Marc

    2011-01-01

    Chondrules are the major high temperature components of chondritic meteorites which accreted a few millions years after the oldest solids of the solar system, the calcium-aluminum-rich inclusions, were condensed from the nebula gas. Chondrules formed during brief heating events by incomplete melting of solid dust precursors in the protoplanetary disk. Petrographic, compositional and isotopic arguments allowed the identification of metal-bearing Mg-rich olivine aggregates among the precursors of magnesian type I chondrules. Two very different settings can be considered for the formation of these Mg-rich olivines: either a nebular setting corresponding mostly to condensation-evaporation processes in the nebular gas or a planetary setting corresponding mostly to differentiation processes in a planetesimal. An ion microprobe survey of Mg-rich olivines of a set of type I chondrules and isolated olivines from unequilibrated ordinary chondrites and carbonaceous chondrites revealed the existence of several modes in the distribution of the ∆17O values and the presence of a large range of mass fractionation (several ‰) within each mode. The chemistry and the oxygen isotopic compositions indicate that Mg-rich olivines are unlikely to be of nebular origin (i.e., solar nebula condensates) but are more likely debris of broken differentiated planetesimals (each of them being characterized by a given ∆17O). Mg-rich olivines could have crystallized from magma ocean-like environments on partially molten planetesimals undergoing metal-silicate differentiation processes. Considering the very old age of chondrules, Mg-rich olivine grains or aggregates might be considered as millimeter-sized fragments from disrupted first-generation differentiated planetesimals. Finally, the finding of only a small number of discrete ∆17O modes for Mg-rich olivines grains or aggregates in a given chondrite suggests that these shattered fragments have not been efficiently mixed in the disk and

  8. Diffusion of Hydrogen in Iron-Bearing Olivine at 3 GPa

    NASA Astrophysics Data System (ADS)

    Demouchy, S. A.; Thoraval, C.; Bolfan-Casanova, N.; Manthilake, G. M.

    2015-12-01

    Physical and chemical properties of Earth's mantle are affected by the interactions with volatiles, and especially by water and water-derived species. Thus, the characterization of solubility and kinetics of incorporation for hydrogen in nominally anhydrous minerals is important to understand the behavior of Earth's deep material under hydrous conditions. Experimental studies on the olivine-water system indicate that significant amounts of hydrogen can be incoporated within olivine as point defects. Extending previous studies, we have focused on the kinetics of hydrogen diffusion in the iron-bearing olivine-water system, performing experiments of hydrogenation of crystallographically oriented olivine single crystals using multi-anvils apparatus at high temperature (900-1200°C) and high pressure (3 GPa). We use polarized Fourier transform infrared spectroscopy to characterize the speciation and the quantify the mobility water-derived defects in olivine, to determine diffusion coefficients under upper mantle conditions. Hydrogen diffusivities are obtained by fitting the hydrogen content measured as a function of position along [100] and [001] direction of the olivine sample, by a 1D and 3D numerical models of diffusion, Our current results indicate that incorporation of hydroxyl species into iron-bearing olivine is a one-stage process with hydrogen chemical diffusion coefficients around 2.10-12 m2/s at 900 °C parallel to [001] (with E // to [001]). The diffusivities are in the same order of magnitude than previous results from iron-bearing olivine at low pressure. The analysis of the different concentration profiles show an anisotropy of diffusion, with diffusion parallel to [001] faster than [100]. Consequences for electrical conductivity in the uppermost mantle will be discussed. This study was financially supported by ANR JCJC "HyDeep" awarded to NBC.

  9. Chemical zoning and homogenization of olivines in ordinary chondrites and implications for thermal histories of chondrules

    NASA Technical Reports Server (NTRS)

    Miyamoto, Masamichi; Mckay, David S.; Mckay, Gordon A.; Duke, Michael B.

    1986-01-01

    The extent and degree of homogenization of chemical zoning of olivines in type 3 ordinary chondrites is studied in order to obtain some constraints on cooling histories of chondrites. Based on Mg-Fe and CaO zoning, olivines in type 3 chondrites are classified into four types. A single chondrule usually contains olivines with the same type of zoning. Microporphyritic olivines show all four zoning types. Barred olivines usually show almost homogenized chemical zoning. The cooling rates or burial depths needed to homogenize the chemical zoning are calculated by solving the diffusion equation, using the zoning profiles as an initial condition. Mg-Fe zoning of olivine may be altered during initial cooling, whereas CaO zoning is hardly changed. Barred olivines may be homogenized during initial cooling because their size is relatively small. To simulated microporphyritic olivine chondrules, cooling from just below the liquidus at moderately high rates is preferable to cooling from above the liquidus at low rates. For postaccumulation metamorphism of type 3 chondrites to keep Mg-Fe zoning unaltered, the maximum metamorphic temperature must be less than about 400 C if cooling rates based on Fe-Ni data are assumed. Calculated cooling rates for both Fa and CaO homogenization are consistent with those by Fe-Ni data for type 4 chondrites. A hot ejecta blanket several tens of meters thick on the surface of a parent body is sufficient to homogenize Mg-Fe zoning if the temperature of the blanket is 600-700 C. Burial depths for petrologic types of ordinary chondrites in a parent body heated by Al-26 are broadly consistent with those previously proposed.

  10. The problem of the origin of symplectites in olivine-bearing lunar rocks

    NASA Technical Reports Server (NTRS)

    Bell, P. M.; Mao, H. K.; Roedder, E.; Weiblen, P. W.

    1975-01-01

    In a study of its origin in olivine-bearing lunar rocks, symplectite is grouped into the following types: (1) very abundant blebs in olivine phenocrysts, (2) scattered blebs in dunite, (3) scattered elongated masses along grain boundaries in troctolite, (4) scattered mosaic assemblages of coarser minerology along grain boundaries, (5) very abundant needle-like arrays, and (6) very abundant grains dispersed in rows. Four theories are proposed to explain the various symplectite distributions.

  11. A Tale of Two Olivines: Magma Ascent in the Auckland Volcanic Field, New Zealand

    NASA Astrophysics Data System (ADS)

    Smid, E. R.; McGee, L. E.; Smith, I. E.; Lindsay, J. M.

    2013-12-01

    The Auckland Volcanic Field (AVF) is a nephelinitic to subalkali basaltic monogenetic field centered on the city of Auckland, New Zealand. Lavas are olivine-phyric, and the deposits of several volcanoes in the field contain olivine crystals with chrome spinel (Cr-spinel) inclusions. Microprobe analyses show at least two populations of olivine, categorised by their Mg# and their spinel inclusion compositions: the first has olivines that are euhedral, have compositions slightly less forsteritic than expected for whole rock Mg#, and have Cr-spinel inclusions with relatively low Cr2O3 contents of ~20%. These are interpreted as antecrysts inherited from the mantle source that yielded their host magma. The second population is characterised by olivines that are sub- to euhedral, are significantly more forsteritic than expected from their host whole rock Mg#, and have Cr-spinel inclusons with relatively high Cr2O3 contents of ~50%. These are interpreted as xenocrysts. The composition of these high Cr2O3 spinels very closely resembles the composition of spinels within olivines in dunite sampled from the Dun Mountain Ophiolite on the South Island of New Zealand. The northward extension of the Dun Mountain complex beneath the North Island is defined by the Junction Magnetic Anomaly, marking a crustal terrane boundary that underlies the Auckland Volcanic Field. These data indicate that the magmas that have risen to produce the volcanoes of the Auckland Volcanic Field have carried crystals from an underlying ultramafic crust as well as from their asthenospheric source. Euhedral olivine crystals which do not contain Cr-spinel are also present in AVF lavas and these are interpreted as true phenocrysts that crystallised directly from their host magmas. The lack of reaction textures at crystal margins suggests rapid ascent rates. A crustal origin for the xenocrysts not only has large implications for ascent rate modelling of olivines, but also for the crustal structure of the

  12. Angrite LEW87051: Are the olivines pheno's or xeno's? A continuing story

    NASA Technical Reports Server (NTRS)

    Jurewicz, A. J. G.; Mckay, G. A.

    1993-01-01

    The achondrite LEW87051 is a porphyritic basalt consisting of large subhedral to euhedral zoned olivines in a finer-grained groundmass. The texture of this groundmass looks remarkably like a quenched melt. However, although the rock is clearly igneous, its exact origins and history are under dispute. From petrographic observations, Prinz felt that the large olivines were xenocrysts and that the zoning reflected interaction with an unrelated, CAI-enriched melt. McKay et al. was able to model the olivines as phenocrysts, whose zoning was the result of a parent melt that changed in composition as material crystallized, e.g., fractional crystallization in a closed system, and calculated a parent melt composition. Jurewicz and McKay compared the calculated parent melt composition with actual partial melts from CV and CM chondrites. They showed that the calculated melt was substantially different from equilibrium melts of these chondrites; however, the LEW87051 groundmass composition was similar to some of the low temperature partial melts, although slightly enriched in AN (or depleted in OL) components. This study presents the results of an independent petrologic look at other olivines in LEW87051 and the preliminary results of a quantitative model for the major zoning in these olivines as diffusive-exchange with an olivine-saturated, low temperature angritic melt.

  13. Characterization and petrologic interpretation of olivine-rich basalts at Gusev Crater, Mars

    USGS Publications Warehouse

    McSween, H.Y.; Wyatt, M.B.; Gellert, Ralf; Bell, J.F.; Morris, R.V.; Herkenhoff, K. E.; Crumpler, L.S.; Milam, K.A.; Stockstill, K.R.; Tornabene, L.L.; Arvidson, R. E.; Bartlett, P.; Blaney, D.; Cabrol, N.A.; Christensen, P.R.; Clark, B. C.; Crisp, J.A.; Des Marais, D.J.; Economou, T.; Farmer, J.D.; Farrand, W.; Ghosh, A.; Golombek, M.; Gorevan, S.; Greeley, R.; Hamilton, V.E.; Johnson, J. R.; Joliff, B.L.; Klingelhofer, G.; Knudson, A.T.; McLennan, S.; Ming, D.; Moersch, J.E.; Rieder, R.; Ruff, S.W.; Schrorder, C.; de Souza, P.A.; Squyres, S. W.; Wanke, H.; Wang, A.; Yen, A.; Zipfel, J.

    2006-01-01

    Rocks on the floor of Gusev crater are basalts of uniform composition and mineralogy. Olivine, the only mineral to have been identified or inferred from data by all instruments on the Spirit rover, is especially abundant in these rocks. These picritic basalts are similar in many respects to certain Martian meteorites (olivine-phyric shergottites). The olivine megacrysts in both have intermediate compositions, with modal abundances ranging up to 20-30%. Associated minerals in both include low-calcium and high-calcium pyroxenes, plagioclase of intermediate composition, iron-titanium-chromium oxides, and phosphate. These rocks also share minor element trends, reflected in their nickel-magnesium and chromium-magnesium ratios. Gusev basalts and shergottites appear to have formed from primitive magmas produced by melting an undepleted mantle at depth and erupted without significant fractionation. However, apparent differences between Gusev rocks and shergottites in their ages, plagioclase abundances, and volatile contents preclude direct correlation. Orbital determinations of global olivine distribution and compositions by thermal emission spectroscopy suggest that olivine-rich rocks may be widespread. Because weathering under acidic conditions preferentially attacks olivine and disguises such rocks beneath alteration rinds, picritic basalts formed from primitive magmas may even be a common component of the Martian crust formed during ancient and recent times. Copyright 2006 by the American Geophysical Union.

  14. Characterization and Petrologic Interpretation of Olivine-Rich Basalts at Gusev Crater, Mars

    NASA Technical Reports Server (NTRS)

    McSween, H. Y.; Wyatt, M. B.; Gellert, R.; Bell, J. F., III; Morris, R. V.; Herkenhoff, K. E.; Crumpler, L. S.; Milam, K. A.; Stockstill, K. R.; Tornabene, L. L.; Arvidson, R. E.; Bartlett, P.; Blaney, D.; Cabrol, N. A.; Christensen, P. R.; Clark, B. C.; Crisp, A.; DesMarais, D. J.; Economou, T.; Farmer, J. D.; Farrand, W.; Ghosh, A.; Golombek, M.; Gorevan, S.; Greeley, R.

    2006-01-01

    Rocks on the floor of Gusev crater are basalts of uniform composition and mineralogy. Olivine, the only mineral to have been identified or inferred from data by all instruments on the Spirit rover, is especially abundant in these rocks. These picritic basalts are similar in many respects to certain Martian meteorites (olivine-phyric shergottites). The olivine megacrysts in both have intermediate compositions, with modal abundances ranging up to 20-30%. Associated minerals in both include low-calcium and high-calcium pyroxenes, plagioclase of intermediate composition, iron-titanium-chromium oxides, and phosphate. These rocks also share minor element trends, reflected in their nickel-magnesium and chromium-magnesium ratios. Gusev basalts and shergottites appear to have formed from primitive magmas produced by melting an undepleted mantle at depth and erupted without significant fractionation. However, apparent differences between Gusev rocks and shergottites in their ages, plagioclase abundances, and volatile contents preclude direct correlation. Orbital determinations of global olivine distribution and compositions by thermal emission spectroscopy suggest that olivine-rich rocks may be widespread. Because weathering under acidic conditions preferentially attacks olivine and disguises such rocks beneath alteration rinds, picritic basalts formed from primitive magmas may even be a common component of the Martian crust formed during ancient and recent times.

  15. Synthesis of crystallographically oriented olivine aggregates using colloidal processing in a strong magnetic field

    NASA Astrophysics Data System (ADS)

    Koizumi, Sanae; Suzuki, Tohru S.; Sakka, Yoshio; Yabe, Kosuke; Hiraga, Takehiko

    2016-07-01

    This study develops a fabrication technique to obtain Fe-free and Fe-bearing (Fe:Mg = 1:9) olivine aggregates not only with high density and fine grain size but with crystallographic preferred orientation (CPO). A magnetic field (≤12 T) is applied to synthetic, fine-grained (~120 nm), olivine particles dispersed in solvent. The alignment of certain crystallographic axes of the particles with respect to a magnetic direction is anticipated due to magnetic anisotropy of olivine. The dispersed particles are gradually consolidated on a porous alumina mold covered with a solid-liquid separation filter during drainage of the solvent. The resultant aligned consolidated aggregate is then isostatically pressed and vacuum sintered. We find that (1) preparation of fully reacted olivine particles, with less propensity to coalesce; (2) preparation of a suspension with highly dispersed particles; and (3) application of a certain strength of the magnetic field are essential to obtain well-sintered and well-aligned aggregates. High density (i.e., <1 vol% porosity) and fine grain size (~1 μm) Fe-free and Fe-bearing olivine aggregates were successfully synthesized with uniaxially aligned a- and c-axes, respectively. Attempts to uniaxially align the magnetization hard axis and to triaxially align Fe-bearing olivine by rotating the suspension in the magnetic field succeeded in obtaining weakly developed CPO aggregates.

  16. Structural and Electrochemical Characterization of Lithium Transition Metal Phosphates

    NASA Astrophysics Data System (ADS)

    Hashambhoy, Ayesha Maria

    The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization of half the Li atoms with Fe and half with Mn. Following this work, pure LiMnPO 4 was explored. LiMnPO4 was successfully fabricated using rapid, solid state microwave irradiation. Three classes of materials were prepared to study the effects of particle size, carbon coating, and electrolytic environment on rate capability. Reduction in particle size, carbon coating, and the aqueous electrolyte environment provided the most favorable conditions for performance enhancement. Based on the initial promising results of solid state microwave synthesis, further studies were conducted to optimize irradiation parameters. C-LiMnPO 4 fabricated at 200W for 5.0 minutes demonstrated the most superior rate capability. This material attained its full theoretical specific capacity, showing promise for the advancement of materials fabricated via this method.

  17. Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures

    NASA Technical Reports Server (NTRS)

    Longazo, Teresa G.; Wentworth, Susan J.; Clemett, Simon J.; Southam, Gordon; McKay, David S.

    2001-01-01

    We are investigating the weathering of silicate minerals by both purely inorganic, and biologically mediated processes using field-emission scanning electron microscopy (FESEM) and energy dispersive x-ray spectroscopy (EDS). By resolving surface textures and chemical compositions of weathered surfaces at the sub-micron scale we hope to be able to distinguish abiotic from biotic weathering processes and so establish a new biosignature applicable to the study of astromaterials including but not limited to the Martian meteorites. Sterilized olivine grains (San Carlos, Arizona) no more than 1-2 mm in their longest dimension were optically assayed to be uniform in color and free of inclusions were selected as weathering subjects. Prior to all experiments surface morphologies and Fe/Mg ratios were determined for each grain using FE-SEM and EDS. Experiments were divided into two categories abiotic and biotic and were compared with "naturally" weathered samples. For the preliminary experiments, two trials (open and closed to the ambient laboratory environment) were performed under abiotic conditions, and three trials under biotic conditions (control, day 1 and day 2). The open system abiotic trials used sterile grains heated at 98 C and 200 C for both 24 and 48 hours in 1L double distilled de-ionized water. The closed system abiotic trials were conducted under the same conditions but in a sealed two layer steel/Teflon "bomb" apparatus. The biotic trials used sterile grains mounted in a flow-through device attached to a wellhead on the Columbia River aquifer. Several discolored, altered, grains were selected to document "natural" weathering surface textures for comparison with the experimental samples. Preliminary results indicate there are qualitative differences in weathered surface textures among all the designed experiments. The olivine grains in abiotic trials displayed etching, pitting, denticulate margins, dissolution and clay formation. The scale of the features

  18. Diffusive Fractionation of Lithium Isotopes in Olivine Grain Boundaries

    NASA Astrophysics Data System (ADS)

    Homolova, V.; Watson, E. B.

    2012-12-01

    Diffusive fractionation of isotopes has been documented in silicate melts, aqueous fluids, and single crystals. In polycrystalline rocks, the meeting place of two grains, or grain boundaries, may also be a site of diffusive fractionation of isotopes. We have undertaken an experimental and modeling approach to investigate diffusive fractionation of lithium (Li) isotopes by grain boundary diffusion. The experimental procedure consists of packing a Ni metal capsule with predominantly ground San Carlos olivine and subjecting the capsule to 1100C and 1GPa for two days in a piston cylinder apparatus to create a nominally dry, 'dunite rock'. After this synthesis step, the capsule is sectioned and polished. One of the polished faces of the 'dunite rock' is then juxtaposed to a source material of spodumene and this diffusion couple is subject to the same experimental conditions as the synthesis step. Li abundances and isotopic profiles (ratios of count rates) were analyzed using LA-ICP-MS. Li concentrations linearly decrease away from the source from 550ppm to the average concentration of the starting olivine (2.5ppm). As a function of distance from the source, the 7Li/6Li ratio decreases to a minimum before increasing to the background ratio of the 'dunite rock'. The 7Li/6Li ratio minimum coincides with the lowest Li concentrations above average 'dunite rock' abundances. The initial decrease in the 7Li/6Li ratio is similar to that seen in other studies of diffusive fractionation of isotopes and is thought to be caused by the higher diffusivity (D) of the lighter isotope relative to the heavier isotope. The relationship between D and mass (m) is given by (D1/D2) =(m2/m1)^β, where β is an empirical fractionation factor; 1 and 2 denote the lighter and heavier isotope, respectively. A fit to the Li isotopic data reveals an effective DLi of ~1.2x10^-12 m/s^2 and a β of 0.1. Numerical modelling was utilized to elucidate the relationship between diffusive fractionation

  19. Molecular Dynamics Simulations of Olivine-Silicate Melt Interfaces

    NASA Astrophysics Data System (ADS)

    Gurmani, Samia; Jahn, Sandro; Brasse, Heinrich; Schilling, Frank R.

    2010-05-01

    Partially molten rocks are important constituents of the Earth's crust and mantle. Their properties depend not only on the chemistry and mineralogy but also on the fraction and distribution of melt or fluid. Partially molten rocks strongly influence the chemical transport in the Earth and geodynamics. We model a partially molten rock on the atomic scale by confining a silicate melt of MgSiO3 composition between Mg2SiO4 olivine crystals. Molecular dynamics simulation is used to study the atomic scale structure and respective transport properties at the interfaces. To represent the atomic interaction, we use an advanced ionic model that accounts for anion polarization and shape deformations (Jahn and Madden, 2007). We construct interfaces between silicate melt layers of different thickness (1.85nm & 3.7nm) and mineral surfaces with different crystal orientations ((010), (001) and (100)). From the particle trajectories we derive various properties like charge density, cation coordination, connectivity of SiO4 tetrahedra and self diffusion coefficients. By adding some (Al, Ca) impurities to the system, the response to different chemical compositions is studied. To obtain a stable solid-melt interface, a temperature of 2000K is chosen. Simulations are performed at ambient pressure. We examine how the chemical composition and the self-diffusion coefficients vary across the interface. Our results indicate that with increase of surface energy, the self-diffusion coefficients of the various species decrease. This may be related to the stronger interaction of the crystal surface with the melt when the surface energy is high, which leads to more structured melt close to the interface. In conclusion, our simulations provide insight into the relation between atomic scale structure and transport properties in partially molten rocks. References S. Jahn and P.A. Madden (2007) Modeling Earth materials from crustal to lower mantle conditions: A transferable set of interaction

  20. Reaction rim growth on olivine in silicic melts: Implications for magma mixing

    USGS Publications Warehouse

    Coombs, M.L.; Gardner, J.E.

    2004-01-01

    Finely crystalline amphibole or pyroxene rims that form during reaction between silicic host melt and cognate olivine xenocrysts, newly introduced during magma mixing events, can provide information about the timing between mixing and volcanic eruptions. We investigated rim growth experimentally by placing forsteritic olivine in rhyolitic and rhyodacitic melts for times between 25 and 622 h at 50 and 150 MPa, H2O-saturated, at the Ni-NiO buffer. Rims of orthopyroxene microlites formed from high-silica rhyolite and rhyodacite melts at 885??C and 50 MPa, and in the rhyolite at 150 MPa and 885??C. Rims of amphibole with lesser orthopyroxene formed in the rhyolite at 150 MPa and 800??C and in the rhyodacite at 150 MPa and 885??C. Irregular, convolute olivine edges and mass balance between olivine, melt, and rim phases show that olivine partly dissolved at all conditions. Iron-rich zones at the exteriors of olivines, which increased in width parabolically with time, show that Fe-Mg interdiffusion occurring in olivines was not outpaced by olivine dissolution. Linear increases of the square of rim widths with time suggest that diffusion within the melt is the rate-controlling process for olivine dissolution and rim growth. Rims grew one-half to one order-of-magnitude faster when melt water contents were doubled, unless conditions were far above the liquidus. Rim growth rate in rhyolite increases from 0.055 ?? 0.01 ??m2/h at 885 ??C and 50 MPa to 0.64 ?? 0.13 ??m2/h at 800 ??C and 150 MPa. Melt composition has a lesser effect on rim growth rates, with growth rate increasing as melt SiO2 content decreases. Pyroxene rims on olivines in andesite erupted from Arenal volcano (Costa Rica) grew at a rate of 3.0 ?? 0.2 ??m2/h over an eleven-year period. This rate is faster than those of the experiments due to lower melt viscosity and higher temperatures, and suggests that a magma mixing event preceded the start of the eruption by days.

  1. Role of olivine cumulates in destabilizing the flanks of Hawaiian volcanoes

    USGS Publications Warehouse

    Clague, D.A.; Denlinger, R.P.

    1994-01-01

    The south flank of Kilauea Volcano is unstable and has the structure of a huge landslide; it is one of at least 17 enormous catastrophic landslides shed from the Hawaiian Islands. Mechanisms previously proposed for movement of the south flank invoke slip of the volcanic pile over seafloor sediments. Slip on a low friction de??collement alone cannot explain why the thickest and widest sector of the flank moves more rapidly than the rest, or why this section contains a 300 km3 aseismic volume above the seismically defined de??collement. It is proposed that this aseismic volume, adjacent to the caldera in the direction of flank slip, consists of olivine cumulates that creep outward, pushing the south flank seawards. Average primary Kilauea tholeiitic magma contains about 16.5 wt.% MgO compared with an average 10 wt.% MgO for erupted subaerial and submarine basalts. This difference requires fractionation of 17 wt.% (14 vol.%) olivine phenocrysts that accumulate near the base of the magma reservoir where they form cumulates. Submarine-erupted Kilauea lavas contain abundant deformed olivine xenocrysts derived from these cumulates. Deformed dunite formed during the tholeiitic shield stage is also erupted as xenoliths in subsequent alkalic lavas. The deformation structures in olivine xenocrysts suggest that the cumulus olivine was densely packed, probably with as little as 5-10 vol.% intercumulus liquid, before entrainment of the xenocrysts. The olivine cumulates were at magmatic temperatures (>1100??C) when the xenocrysts were entrained. Olivine at 1100??C has a rheology similar to ice, and the olivine cumulates should flow down and away from the summit of the volcano. Flow of the olivine cumulates places constant pressure on the unbuttressed seaward flank, leading to an extensional region that localizes deep intrusions behind the flank; these intrusions add to the seaward push. This mechanism ties the source of gravitational instability to the caldera complex and deep

  2. CO2-induced small water solubility in olivine and implications for properties of the shallow mantle

    NASA Astrophysics Data System (ADS)

    Yang, Xiaozhi; Liu, Dingding; Xia, Qunke

    2014-10-01

    H2O and CO2 are important components of fluids in the mantle at ∼30-150 km depth, and may affect strongly water dissolution in nominally anhydrous olivine; however, available experimental hydrogenation of olivine has been nearly exclusively carried out in coexistence with H2O (CO2-free). In this study, the effect of CO2 on water solubility in olivine has been investigated by H-annealing natural olivine under peridotite- and fluid-saturated conditions. Experiments were conducted at 1.5-5 GPa and 1100-1300 °C, with oxygen fugacity controlled by Ni-NiO and with either H2O or H2O-CO2 as buffering fluid. The olivine shows no change in composition during the experiments. The infrared spectra of the hydrated olivine are characterized by prominent OH bands from ∼3650 to 3000 cm in all the runs, at both high frequency (>3450 cm) and low frequency (<3450 cm), and the H2O solubility is ∼120-370 ppm for the olivine in coexisting with H2O, and ∼65-180 ppm for the olivine in coexisting with H2O-CO2. When CO2 is present in the buffering fluid, the H2O solubility of olivine is reduced by a factor of ∼2, due to effect on the partitioning of water between minerals and coexisting fluid, and the measured H2O solubility shows independence on fluid composition (the molar ratio of CO2 to CO2 + H2O at ∼0.2-0.5) given pressure, temperature and oxygen fugacity. Olivine equilibrated in the shallow mantle is probably dominated by OH groups in the wavenumber ∼3650-3000 cm, and the intensity of OH bands at low frequency may be higher than or comparable to those at higher frequencies. The storage capacity of water in the shallow mantle in previous estimates may have been overestimated by a factor of at least ∼4 if the observed effect of CO2 on water solubility is correct. Our results have profound influence on understanding partial melting, electrical conductivity anomalies and metasomatism in the shallow mantle.

  3. Experimental Partitioning of Cr(3+) and Sc(3+) into Olivine: Mechanisms and Implications

    NASA Technical Reports Server (NTRS)

    Jones, John; Mackwell, S. J.

    2006-01-01

    Olivine (Mg, Fe)Si2O4 does not, by stoichiometry, accept cations such as Sc(3+) or Cr(3+). However, the partition coefficients of Sc and Cr between olivine and liquid are significant 0.2-1.0. We have measured Cr(3+) partition coefficients of near unity and have grown olivines with nearly 3 wt.% Sc2O3. Therefore, there must be a simple means of charge balancing 3+ ions in a crystal structure that was obviously not designed to receive other than 2+ ions on the olivine M sites. The simplest explanation is that two 3+ ions enter the olivine structure by displacing three 2+ ions and creating an M site vacancy. Even this explanation has difficulties. For minor elements in our experiments (1 wt.%) the odds of a minor element 3+ ion finding a second 3+ for charge balance are of the order of 100:1 against. Because of the reducing conditions of our experiments, Fe(3+) will not suffice; and Al(3+) is not in sufficient quantity in olivine for charge balance. Therefore, Cr or Sc must, in effect, charge balance itself. For true trace elements, the problem is compounded many times. For an ion at the 10 ppm level the chances of finding a second (for example) Sc ion is approx.10(exp 5):1 against. Of course, any other 3+ ion would suffice but comparisons between percent level doping experiments and trace level partitioning indicate that Henry s law is obeyed. This implies that the same substitution mechanism occurs at both the percent and tens of ppm levels. There are two simple solutions to this problem: (i) The electrical conductivity of olivine is such that charge balance need not be local. This requires substantial domains within the olivine crystal in electrical contact by migration of vacancies or electronic defects. (ii) The 3+ cation brings along its own charge-balancing ion because it existed as a dimer in the silicate liquid. Olivine is not a true insulator but is actually a p-type semiconductor. Even so, electrical communication by this means is unlikely over the tens or

  4. Olivine-rich troctolites from the Internal Liguride ophiolites (Northern Apennine, Italy)

    NASA Astrophysics Data System (ADS)

    Renna, M. R.; Tribuzio, R.

    2009-04-01

    The Internal Liguride ophiolites from Northern Apennine represent an intra-oceanic domain of the Middle to Late Jurassic Ligure-Piemontese basin. These ophiolites are characterised by morphological highs made of gabbroic rocks preserving intrusive relations with mantle peridotites (Cortesogno et al. 1987). The gabbroic plutons consist mostly of coarse-grained gabbros to olivine-gabbros and contain, at different stratigraphic levels, sill-like lenses of olivine-rich troctolites. These lenses are commonly tens of metres in thickness and hundred of metres in length. The olivine-rich troctolites are mainly composed of rounded to polygonal olivine (generally 70-90 vol%), anhedral plagioclase, minor poikilitic clinopyroxene and accessory spinel (Bezzi and Piccardo 1971). They are locally associated with layers (up to tens of centimetres in thickness) that vary modally from troctolite to anortosite and chromitite. One of the studied olivine-rich troctolite lenses shows a metre-scale layer displaying a "harrisite" pegmatoid texture, in which huge skeletal olivines (up to 30 cm) are intergrown with plagioclase (Bezzi and Piccardo 1971). In addition, gabbroic dykelets (mm- to cm-scale in thickness) displaying fuzzy contacts towards the olivine-rich troctolites occur in places. Olivine from the olivine-rich troctolites has forsterite ranging from 88 to 85 mol% and NiO concentrations of 0.3 wt%. Spinel has Cr# and TiO2 varying from 54 to 46 and from 2.7 to 1.0 wt%, respectively. Clinopyroxene displays Mg# ranging from 90 to 86 and high amounts of Al, Cr and Ti; its REE pattern is LREE-depleted with nearly flat HREE, thus showing equilibrium with MORB-type melts. Increasing total REE abundances in clinopyroxene are associated with the development of negative Eu anomaly. The outermost rim of clinopyroxene is Al- and Cr-depleted and Ti-enriched compared to the core. Accessory Cr- and Ti-rich amphibole is locally present, as rim around spinel and as inclusion within spinel. Other

  5. Experimental constraints on formation of hematite in olivine at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Zhang, Yanfei; Wang, Chao; Wu, Yao; Liu, Wenlong; Jin, Zhenmin

    2015-10-01

    Iron-rich oxides, such as magnetite or hematite, have been reported in olivine grains in many orogenic garnet peridotites from continental collision zones. Whether these iron-rich minerals originate from dry oxidation, dehydrogenation-oxidation or exsolution from a precursor wadsleyite phase is debatable. This paper explores high-pressure and high-temperature experiments in a hydrous harzburgite system, by taking advantage of electron backscattered diffraction (EBSD) analyses, to examine the formation of hematite in olivine. Experimental results show that hematite can be formed within olivine grains at pressures >6 GPa and temperatures in the 1073-1473 K range. EBSD analysis suggests that hematite rods (not associated with clinopyroxene) and host olivine have the following crystallographic relations: < 0001 rangle _{{Hem}} // [100]_{{Ol}} , < 10{-}10rangle _{{Hem}} //[001]_{{Ol}} , < 11{-}20rangle _{{Hem}} //[010]_{{Ol}} , which are consistent with those observed in natural garnet peridotite from the Dabie-Sulu ultra-high-pressure (UHP) metamorphic terrane. It is postulated that both hydroxide (OH-) and hydrogen (H+) ions have the potential to oxidize Fe2+ to Fe3+, followed by rapid dehydrogenation and slow Fe diffusion, thus forming hematite within the olivine grains. It is proposed that dehydrogenation-oxidation is the most likely formation mechanism of hematite inclusions within olivine, with the following two requirements: an ample amount of H2O and specific P- T conditions (>6 GPa, at 1073 K). Such conditions are consistent with those calculated in natural garnet peridotites from the Dabie-Sulu UHP metamorphic terranes. The present study also indicates that hematite (or magnetite?) inclusions in olivine contain important clues about the tectonic evolution of UHP rocks in continental crust collision zones.

  6. Temperature Dependence and Recoil-free Fraction Effects in Olivines Across the Mg-Fe Solid Solution

    NASA Technical Reports Server (NTRS)

    Sklute, E. C.; Rothstein, Y.; Dyar, M. D.; Schaefer, M. W.; Menzies, O. N.; Bland, P. A.; Berry, F. J.

    2005-01-01

    Olivine and pyroxene are the major ferromagnesian minerals in most meteorite types and in mafic igneous rocks that are dominant at the surface of the Earth. It is probable that they are the major mineralogical components at the surface of any planetary body that has undergone differentiation processes. In situ mineralogical studies of the rocks and soils on Mars suggest that olivine is a widespread mineral on that planet s surface (particularly at the Gusev site) and that it has been relatively unaffected by alteration. Thus an understanding of the characteristics of Mossbauer spectra of olivine is of great importance in interpreting MER results. However, variable temperature Mossbauer spectra of olivine, which are needed to quantify recoil-free fraction effects and to understand the temperature dependence of olivine spectra, are lacking in the literature. Thus, we present here a study of the temperature dependence and recoil-free fraction of a series of synthetic olivines.

  7. Melt/rock reaction at oceanic peridotite/gabbro transition as revealed by trace element chemistry of olivine

    NASA Astrophysics Data System (ADS)

    Rampone, Elisabetta; Borghini, Giulio; Godard, Marguerite; Ildefonse, Benoit; Crispini, Laura; Fumagalli, Patrizia

    2016-10-01

    Several recent studies have documented that reactions between melt and crystal mush in primitive gabbroic rocks (via reactive porous flow) have an important control in the formation of the lower oceanic crust and the evolution of MORBs. In this context, olivine-rich rocks can form either by fractional crystallization of primitive melts or by open system reactive percolation of pre-existing (possibly mantle-derived) olivine matrix. To address this question, we performed in-situ trace element analyses (by LA-ICP-MS) of olivine from the Erro-Tobbio ophiolite Unit (Ligurian Alps), where mantle peridotites show gradational contacts with an hectometer-scale body of troctolites and plagioclase wehrlites, and both are cut by later decameter-wide lenses and dykes of olivine gabbros. Previous studies inferred that troctolites and olivine gabbros represent variably differentiated crystallization products from primitive MORB-type melts. Olivines in the three rock types (mantle peridotites, troctolites, olivine gabbros) exhibit distinct geochemical signature and well-defined elemental correlations. As expected, compatible elements (e.g. Ni) show the highest concentrations in peridotites (2580-2730 ppm), intermediate in troctolites (2050-2230 ppm) and lowest in gabbros (1355-1420 ppm), whereas moderate incompatible elements (e.g. Mn, Zn) show the opposite behaviour. By contrast, highly incompatible elements like Zr, Hf, Ti, HREE are variably enriched in olivines of troctolites, and the enrichment in absolute concentrations is coupled to development of significant HFSE/REE fractionation (ZrN/NdN up to 80). AFC modelling shows that such large ZrN/NdN ratios in olivines are consistent with a process of olivine assimilation and plagioclase crystallization at decreasing melt mass, in agreement with textural observations. In-situ trace element geochemistry of olivine, combined with microstructural investigations, thus appears a powerful tool to investigate reactive percolation and the

  8. Olivine + halides: a recipe for iron mobilization in volcanic ash?

    NASA Astrophysics Data System (ADS)

    Hoshyaripour, G.; Hort, M. K.; Langmann, B.

    2013-12-01

    ). Thus, the presence of the reduced iron species in the mineral assemblage seems to be more favorable for the soluble iron production. We conclude that bio-available iron production is weakly correlated with the tectonic setting and is instead controlled by the halide content of the eruption plume and the oxidation state of the iron at the ash mineral assemblage (e.g. presence of olivine). This hypothesis could satisfactorily explain the extraordinary iron release from the ash of Hekla eruption in 2000 and also the fertilization impact caused by the ash erupted from Kasatochi in 2008.

  9. In situ SIMS oxygen isotope analysis of olivine in the Tibetan mantle xenoliths

    NASA Astrophysics Data System (ADS)

    Zhao, Zhidan; Zhu, Di-Cheng; Liu, Dong; Mo, Xuanxue

    2016-04-01

    Although the mantle-derived xenoliths from Lhasa terrane provide a means of directly investigating the mantle underlying the southern part of the plateau, they were rarely found in the region. The only case of mantle xenoliths came from the Sailipu ultrapotassic volcanic rocks, erupted at ˜17 Ma, which have indicated that the subcontinental mantle of southern Tibetan Plateau is hot and strongly influenced by metasomatism (Zhao et al., 2008a, b; Liu et al., 2011). A further study by Liu et al.(2014) of in-situ oxygen isotope of olivine crystals in Sailipu mantle xenoliths identify a metasomatized mantle reservoir that interpreted as the sub-arc lithospheric mantle, with anomalously enriched oxygen isotopes (δ18O=8.03). Here we present oxygen isotopes data on the Sailipu mantle xenolith olivines, using different method of sample preparation. Mantle xenoliths (less than 1 cm in diameter) together originally with their host volcanic rocks were prepared in epoxy adjacent to grains of a San Carlos olivine intralaboratory standard and then polished to a flat and smooth surface. Oxygen isotope compositions of olivines occurs both in mantle xenolith and as phenocryst in the host rock, were analyzed in situ using CAMECA SIMS-1280 ion microprobe at the Institute of Geology and Geophysics, Chinese Academy of Sciences. We also performed traditional oxygen isotope analysis on three olivine phenocrysts separates from the host lava. Our new data show: (1) The mantle xenolith olivines have typical mantle oxygen isotopic composition (δ18O=4.8-8.0‰ with average of 5.5±0.2‰ n=105) with variety Fo#(78-90), (2) Oxygen isotopes of situ olivine phenocrysts in the Sailipu lavas (δ18O=7.1-9.2‰ Fo#=70-84, n=66), are similar to that of the whole rock (δ18O=7.0-9.4‰ Fo#=64-74, n=8, Zhao et al., 2009), and three olivine phenocryst grains (δ18O=7.2-7.8); (3) The intralaboratory standard of San Carlos olivine can be a suitable standard using for analyzing olivines with Fo not only

  10. Fayalitic olivine in CV3 chondrite matrix and dark inclusions: A nebular origin

    NASA Astrophysics Data System (ADS)

    Weisberg, Michael K.; Prinz, Martin

    1998-09-01

    Fayalitic olivine (Fa>32) is the major component of the matrices and Dark Inclusions (DI) of CV3 and other unequilibrated chondrites. It occurs most commonly as rims, veins and halos in and around chondrule silicates in the Allende-type (CV3OxA) chondrites and to a much lesser extent in the reduced (CV3R) and Bali-type (CV3OxB) chondrites. The olivines have distinctive platy, tabular and lath- or irregular-shaped crystals, with the ratio the two types varying widely. In CV3OxB chondrites, matrix fayalitic olivines range up to Fa99.9, whereas in the other CV3 chondrites the range is much smaller. The platy and tabular anisotropic forms of the fayalitic olivines strongly suggest growth from a vapor and the nature of occurrences suggests that CV3 matrices are unequilibrated mixtures of nebular materials. We argue that the parent body hydration/dehydration model has numerous inconsistencies that make this hypothesis highly unlikely. These include: (1) There is no direct evidence linking fayalitic olivine to precursor phyllosilicates. (2) Dehydration of phyllosilicates cannot explain the wide range of morphologies of the fayalitic olivines. (3) Fayalitic olivine clearly predates the formation of the hydrous phases in CV3 chondrites and is one of the phases that breaks down to form phyllosilicates (Keller et al., 1994). (4) The unequilibrated nature of the matrix, including fine scale zoning in 10=B5-sized fayalitic olivine crystals, would not survive the parent body metamorphism required in the dehydration model. (5) A DI in the Ningqiang chondrite contains fayalitic olivine rimmed by glassy and microcrystalline material (Zolensky et al., 1997), which probably formed by radiation damage. This indicates that the fayalitic olivine was exposed to solar radiation in a nebular setting. (6) Some Allende chondrules contain unaltered primary, anhydrous glassy mesostasis in contact with the host matrix (e.g., Ikeda and Kimura, 1995). Chondrule mesostases would not have survived

  11. Observation of the type-E crystallographic preferred orientation of olivine in peridotite from Val Malenco, Italy

    NASA Astrophysics Data System (ADS)

    Jung, H.

    2006-12-01

    Recent experimental studies of olivine at high pressure and high temperature under controlled physical and chemical conditions have shown that crystallographic preferred orientation (CPO) of olivine depends on water content and stress. Under low water content and low stress conditions, olivine [100] axis is aligned subparallel to lineation direction and (010) plane subparallel to shear plane (type-A; Jung and Karato, 2001). In contrast, under moderate water content and low stress conditions, olivine [100] axis is aligned subparallel to lineation direction and (001) plane subparallel to shear plane (type-E; Katayama et al., 2004; Jung et al, 2006). Only a few examples of the type-E CPO of olivine were reported so far. CPOs of olivine in peridotite from Val Malenco, Italy were investigated. The peridotite was partially serpentinized. Two types of CPOs (type-A and E) were observed depending on grain size. Type-A CPO of olivine was observed where grain size was large while type-E CPO of olivine was observed where grain size was small and recrystallized. Two stages of deformation of the peridotie are inferred based on the observed fabrics and previous experimental studies of olivine. The peridotite may be deformed initially under low water content and low stress conditions and deformed later under modedrate water content and low stress conditions. Deformation microstructures of the rock and implications for seismic anisotropy in subduction zones will be discussed.

  12. Olivine in terminal particles of Stardust aerogel tracks and analogous grains in chondrite matrix

    NASA Astrophysics Data System (ADS)

    Frank, David R.; Zolensky, Michael E.; Le, Loan

    2014-10-01

    The dearth of both major and minor element analyses of anhydrous silicate phases in chondrite matrix has thus far hindered their comparison to the Wild 2 samples. We present 68 analyses of olivine (Fa0-97) in the coarse-grained terminal particles of Stardust aerogel tracks and a comprehensive dataset (>103 analyses) of analogous olivine grains (5-30 μm) isolated in CI, CM, CR, CH, CO, CV3-oxidized, CV3-reduced, C3-ungrouped (Acfer 094 and Ningqiang), L/LL 3.0-4, EH3, and Kakangari chondrite matrix. These compositions reveal that Wild 2 likely accreted a diverse assortment of material that was radially transported from various carbonaceous and ordinary chondrite-forming regions. The Wild 2 olivine includes amoeboid olivine aggregates (AOAs), refractory forsterite, type I and type II chondrule fragments and/or microchondrules, and rare relict grain compositions. In addition, we have identified one terminal particle that has no known compositional analog in the meteorite record and may be a signature of low-temperature, aqueous processing in the Kuiper Belt. The generally low Cr content of FeO-rich olivine in the Stardust samples indicates that they underwent mild thermal metamorphism, akin to a petrologic grade of 3.05-3.15.

  13. Using Classical Dispersion Analysis to Extract Peak Parameters, Optical Constants from IR Lab Absorbance Spectra: Olivine

    NASA Astrophysics Data System (ADS)

    Pitman, Karly M.; Dijkstra, C. R.; Hofmeister, A. M.; Speck, A. K.

    2009-05-01

    Laboratory measurements quantifying the effect of Fe substituting for Mg in olivine are needed to distinguish compositional from temperature effects in observational data. Because most olivine samples are too small to acquire reflectivity data used to obtain the optical functions n(λ) and k(λ) needed for radiative transfer models, we apply the principle that classical dispersion theory may be used to determine peak positions, widths, strengths, and n and k estimates from absorption spectra of thin film samples. We study room temperature absorption spectra of a large suite of olivines evenly spaced across Mg and Fe compositions, and isotropic and anisotropic minerals with varying hardness and numbers of spectral bands. For olivine, adding accounting for asymmetric peak shapes does not substantially alter estimates of peak position but increases the error on FWHM and oscillator strengths. Values from classical dispersion fits match published n and k derived from reflectivity (better agreement in k) when the dust proxy is soft and the thickness of the sample is independently constrained. Electronic data and peak parameter trends for the laboratory olivine absorption spectra and the viability of the extracted n and k are discussed with regard to astronomy.

  14. Infrared laboratory absorbance spectra of olivine: using classical dispersion analysis to extract peak parameters

    NASA Astrophysics Data System (ADS)

    Pitman, K. M.; Dijkstra, C.; Hofmeister, A. M.; Speck, A. K.

    2010-07-01

    Laboratory measurements quantifying the effect of Fe substituting for Mg in olivine are needed to distinguish compositional from temperature, grain size and grain shape effects in observational data. To address this need, we study room temperature absorption spectra of a large suite of olivines evenly spaced across Mg and Fe compositions. We apply the principle that classical dispersion theory may be used to determine peak positions as well as peak widths, strengths and possibly optical function (n(λ) and k(λ)) estimates from absorption spectra of thin film samples of these olivines and two additional isotropic and anisotropic minerals with varying hardness and numbers of spectral bands. For olivine, we find that this method provides good estimates of peak position and that accounting for asymmetric peak shapes in this way increases the error on full width at half-maximum and oscillator strengths. Values from classical dispersion fits better match published n and k derived from reflectivity of single crystals when the dust proxy is soft and the thickness of the sample is independently constrained. Electronic data and peak parameter trends for the laboratory olivine absorption spectra and the viability of the extracted n and k are discussed with regard to astronomy.

  15. Shock-induced fine-grained recrystallization of olivine - Evidence against subsolidus reduction of Fe/2+/

    NASA Technical Reports Server (NTRS)

    Ahrens, T. J.; Tsay, F.-D.; Live, D. H.

    1976-01-01

    Electron spin resonance (ESR) studies have been carried out on three single grains of terrestrial olivine (Fo90) shock loaded along the 010 line to peak pressures of 280, 330, and 440 kbar. The results indicate that neither metallic Fe similar to that observed in returned lunar soils nor paramagnetic Fe(3+) caused by oxidation of Fe(2+) has been produced in these shock experiments. Trace amounts of Mn (2+) have been detected in both shocked and unshocked olivine. The ESR signals of Mn(2+) show spectral features which are found to correlate with the degree of shock-induced recrystallization observed petrographically. The increasing mass fraction of recrystallized olivine correlates with increasing shock pressures. This phenomenon is modelled assuming it results from the progressive effect of the shock-induced transformation of the olivine to a yet unknown high-pressure phase and its subsequent reversion to the low-pressure olivine phase. The mass fraction of recrystallized material is predicted to be nearly linear with shock pressure.

  16. Space weathering simulations through controlled growth of iron nanoparticles on olivine

    NASA Astrophysics Data System (ADS)

    Kohout, Tomáš; Čuda, Jan; Filip, Jan; Britt, Daniel; Bradley, Todd; Tuček, Jiří; Skála, Roman; Kletetschka, Gunther; Kašlík, Josef; Malina, Ondřej; Šišková, Karolína; Zbořil, Radek

    2014-07-01

    Airless planetary bodies are directly exposed to space weathering. The main spectral effects of space weathering are darkening, reduction in intensity of silicate mineral absorption bands, and an increase in the spectral slope towards longer wavelengths (reddening). Production of nanophase metallic iron (npFe0) during space weathering plays major role in these spectral changes. A laboratory procedure for the controlled production of npFe0 in silicate mineral powders has been developed. The method is based on a two-step thermal treatment of low-iron olivine, first in ambient air and then in hydrogen atmosphere. Through this process, a series of olivine powder samples was prepared with varying amounts of npFe0 in the 7-20 nm size range. A logarithmic trend is observed between amount of npFe0 and darkening, reduction of 1 μm olivine absorption band, reddening, and 1 μm band width. Olivine with a population of physically larger npFe0 particles follows spectral trends similar to other samples, except for the reddening trend. This is interpreted as the larger, ∼40-50 nm sized, npFe0 particles do not contribute to the spectral slope change as efficiently as the smaller npFe0 fraction. A linear trend is observed between the amount of npFe0 and 1 μm band center position, most likely caused by Fe2+ disassociation from olivine structure into npFe0 particles.

  17. A High Voltage Olivine Cathode for Application in Lithium-Ion Batteries.

    PubMed

    Di Lecce, Daniele; Brescia, Rosaria; Scarpellini, Alice; Prato, Mirko; Hassoun, Jusef

    2016-01-01

    A new olivine composition (i.e., LiFe0.25 Mn0.5 Co0.25 PO4) is proposed as electrode material with increased energy density for application in lithium-ion batteries. The new formulation increases the working voltage and induces different electrochemical behavior with respect to bare olivine materials based on Fe. The study provides deep insight into the features of the Fe(3+) /Fe(2+), Mn(3+)/Mn(2+), and Co(3+)/Co(2+) redox couples within the olivine lattice in terms of electrochemical activity, Li(+) transport properties, and Li-cell behavior. The electrochemical characterization clearly reveals the voltage signatures corresponding to the various metals; however, the Mn(3+)/Mn(2+) process has higher intrinsic polarization with respect to Fe(3+)/Fe(2+) and Co(3+)/Co(2+). This issue is efficiently mitigated by carbon coating the material, resulting in enhanced electrochemical performances.

  18. Low-temperature plasticity of olivine revisited with in situ TEM nanomechanical testing.

    PubMed

    Idrissi, Hosni; Bollinger, Caroline; Boioli, Francesca; Schryvers, Dominique; Cordier, Patrick

    2016-03-01

    The rheology of the lithospheric mantle is fundamental to understanding how mantle convection couples with plate tectonics. However, olivine rheology at lithospheric conditions is still poorly understood because experiments are difficult in this temperature range where rocks and mineral become very brittle. We combine techniques of quantitative in situ tensile testing in a transmission electron microscope and numerical modeling of dislocation dynamics to constrain the low-temperature rheology of olivine. We find that the intrinsic ductility of olivine at low temperature is significantly lower than previously reported values, which were obtained under strain-hardened conditions. Using this method, we can anchor rheological laws determined at higher temperature and can provide a better constraint on intermediate temperatures relevant for the lithosphere. More generally, we demonstrate the possibility of characterizing the mechanical properties of specimens, which can be available in the form of submillimeter-sized particles only. PMID:26998522

  19. Thermal histories of CO3 chondrites - Application of olivine diffusion modelling to parent body metamorphism

    NASA Technical Reports Server (NTRS)

    Jones, Rhian H.; Rubie, David C.

    1991-01-01

    The petrologic sequence observed in the CO3 chondrite group has been suggested to be the result of thermal metamorphism on a parent body. A model developed to examine the possibility that chondrule and matrix olivines equilibrated in situ, during parent body metamorphism is presented. The model considers Fe-Mg interdiffusion between chondrule and matrix olivines. Zoning profiles comparable to those observed in chondrule olivines from partially equilibrated members of the series are reproduced successfully. Metamorphism of CO3 chondrites on a parent body is therefore a viable model for the observed equilibration. Results indicate that peak metamorphic temperatures experienced by the CO3 chondrites were around 500 C, and that the range of peak temperatures between unequilibrated and equilibrated subtypes was relatively narrow, around 100 C.

  20. Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, D. W.; Rumble, D., III

    2006-01-01

    Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with

  1. Beryllium diffusion in olivine: A new tool to investigate timescales of magmatic processes

    NASA Astrophysics Data System (ADS)

    Jollands, Michael C.; Burnham, Antony D.; O'Neill, Hugh St. C.; Hermann, Joerg; Qian, Qing

    2016-09-01

    The diffusion of beryllium (Be) in pure synthetic forsterite (fo100) and San Carlos olivine (fo90) was studied between 950-1475 °C at atmospheric pressure, as a function of silica activity (aSiO2), crystallographic orientation, oxygen fugacity (fO2, for diffusion in San Carlos olivine) and water fugacity (fH2O, at 1.15 GPa pressure (P)). The diffusivity of Be in olivine is faster than that of Mg2+ or Fe2+ but slower than that of H+, and appears to be insensitive to aSiO2, fH2O and P, but is highly anisotropic, with diffusivities described by:

  2. The influence of bulk composition and dynamic melting conditions on olivine chondrule textures

    NASA Technical Reports Server (NTRS)

    Connolly, Harold C., Jr.; Hewins, Roger H.

    1991-01-01

    The effects of the bulk composition and the dynamic melting conditions on the texture of olivine chondrules were investigated in a series of heating experiments. It is shown that variations in the olivine chondrule textures can be produced by varying the FeO/(FeO + MgO) ratio between the average Type IA and Type II chondrule compositions, could affect the texture of a chondrule at a constant initial melting temperature and heating time. A range of the heating times and the masses of precursor spheres caused variations in the degree of melting and in chondrule textures. Chondrule textures were distributed on a graph of initial temperatures vs. FeO/(FeO + MgO) ratios as bands parallel to the olivine disappearance curve. This graph could be used to predict chondrule textures from Fe/(FeO + MgO) ratios at specific initial melting temperatures.

  3. Low-temperature plasticity of olivine revisited with in situ TEM nanomechanical testing.

    PubMed

    Idrissi, Hosni; Bollinger, Caroline; Boioli, Francesca; Schryvers, Dominique; Cordier, Patrick

    2016-03-01

    The rheology of the lithospheric mantle is fundamental to understanding how mantle convection couples with plate tectonics. However, olivine rheology at lithospheric conditions is still poorly understood because experiments are difficult in this temperature range where rocks and mineral become very brittle. We combine techniques of quantitative in situ tensile testing in a transmission electron microscope and numerical modeling of dislocation dynamics to constrain the low-temperature rheology of olivine. We find that the intrinsic ductility of olivine at low temperature is significantly lower than previously reported values, which were obtained under strain-hardened conditions. Using this method, we can anchor rheological laws determined at higher temperature and can provide a better constraint on intermediate temperatures relevant for the lithosphere. More generally, we demonstrate the possibility of characterizing the mechanical properties of specimens, which can be available in the form of submillimeter-sized particles only.

  4. Crystal/liquid partitioning of REE in basaltic systems Extreme fractionation of REE in olivine

    NASA Technical Reports Server (NTRS)

    Mckay, G. A.

    1986-01-01

    The calculation of partial coefficients for Nd, Sm, Gd, and Yb between olivine and synthetic basaltic melts using the percent level doping technique and microprobe analytical techniques is examined. The experimental and analytical procedures are described. The relationship between rare earth elements (REEs) concentrations and crystal margins caused by Rees X-rays from surrounding glass is discussed. Average olivine/liquid distribution coefficients for Nd, Sm, Gd, and Yb for mare and highlands basaltic melts are presented. The data reveal that the distribution coefficients for light REEs are lower than those obtained in previous studies, and the slope of the olivine/liquid distribution coefficient pattern is steeper; potential sources of error in the previous and present studies which could explain the differences in distribution coefficients and slope are investigated.

  5. Peridotite and pyroxenite components in the sources of Grande Comore lavas: evidence from olivine compositions

    NASA Astrophysics Data System (ADS)

    Weiss, Y.; Class, C.; Goldstein, S. L.

    2013-12-01

    Grande Comore (Ngazidja) is the youngest Island of the Comores Archipelego in the Indian Ocean, located in the Somali Basin between Africa and Madagascar. The island formed by two volcanoes. Karthala is an active shield volcano, and La Grille is composed mainly of monogenetic cinder cones. The island represents interaction between a mantle plume and oceanic lithosphere and previous studies suggested, based on the major, trace elements and Sr-Nd-Pb-Os isotopic relationships of the lavas, that the alkali basalts of Karthala reflect mainly plume derived melts, while the basanites of La Grille are the products of interaction of plume melts with the metasomatized oceanic lithosphere. Here we report the chemical composition of olivine phenocrysts of Karthala lavas (5 samples), old Karthala (1) and La Grille (3) that were previously analyzed for their major, trace elements and Sr, Nd, Pb, Os and He isotopic compositions. Olivine phenocrysts from Karthala lavas have higher Mn and Ca, lower Al and slightly lower Ni content compared to olivines from La Grille at similar Mg#. Olivines from ';Old Karthala'are close in composition to those from La Grille and the content of Cr is similar between all three groups. The average Mn/Fe and Ca/Fe ratios of olivines of the samples positive correlate with the Sr-Pb-Os isotope ratios of the corresponding whole rocks, and Karthala has higher values than La Grille. These ratios negatively correlate with Nd-He isotope ratios, as well as with the La/Gd, Gd/Yb and Nb/K of the host lavas. The average Ni/Mg and Al/Mg ratios of the olivines correlate with the isotopic and trace element ratios of the whole rocks as well, but display trends in the opposite direction to the ones observed for Mn/Ca over Fe. Previous studies have proposed that the minor element (Ni, Mn and Ca) composition in olivine can be used to infer the proportions of peridotite vs pyroxenite and thus, the amount of recycled ocean crust in the source lithologies of magmas

  6. Chemical zoning and diffusion of Ca, Al, Mn, and Cr in olivine of springwater pallasite

    NASA Technical Reports Server (NTRS)

    Zhou, Y.; Steele, Ian M.

    1993-01-01

    The pallasites, consisting mainly of Fe-Ni metal and olivine, are thought to represent the interior of a planetary body which slowly cooled from high temperature. Although the olivines are nearly homogeneous, ion microprobe studies revealed variations of Ca, Ti, Co, Cr, and Ni near grain edges. These variations were thought to represent diffusion in response to falling temperature of the parent body. Pallasite cooling rates have been estimated based on kamacite taenite textures but results differ by x100. In principle elemental profiles in olivine can allow estimates of cooling rate if diffusion coefficients are known; in addition, given a cooling rate, diffusion coefficients could be derived. Data are presented which show that apparent diffusion profiles can be measured for Al, Ca, Cr, and Mn which qualitatively agree with expected diffusion rates and have the potential of providing independent estimates of pallasite cooling rates.

  7. Low-temperature plasticity of olivine revisited with in situ TEM nanomechanical testing

    PubMed Central

    Idrissi, Hosni; Bollinger, Caroline; Boioli, Francesca; Schryvers, Dominique; Cordier, Patrick

    2016-01-01

    The rheology of the lithospheric mantle is fundamental to understanding how mantle convection couples with plate tectonics. However, olivine rheology at lithospheric conditions is still poorly understood because experiments are difficult in this temperature range where rocks and mineral become very brittle. We combine techniques of quantitative in situ tensile testing in a transmission electron microscope and numerical modeling of dislocation dynamics to constrain the low-temperature rheology of olivine. We find that the intrinsic ductility of olivine at low temperature is significantly lower than previously reported values, which were obtained under strain-hardened conditions. Using this method, we can anchor rheological laws determined at higher temperature and can provide a better constraint on intermediate temperatures relevant for the lithosphere. More generally, we demonstrate the possibility of characterizing the mechanical properties of specimens, which can be available in the form of submillimeter-sized particles only. PMID:26998522

  8. Comet-like mineralogy of olivine crystals in an extrasolar proto-Kuiper belt.

    PubMed

    de Vries, B L; Acke, B; Blommaert, J A D L; Waelkens, C; Waters, L B F M; Vandenbussche, B; Min, M; Olofsson, G; Dominik, C; Decin, L; Barlow, M J; Brandeker, A; Di Francesco, J; Glauser, A M; Greaves, J; Harvey, P M; Holland, W S; Ivison, R J; Liseau, R; Pantin, E E; Pilbratt, G L; Royer, P; Sibthorpe, B

    2012-10-01

    Some planetary systems harbour debris disks containing planetesimals such as asteroids and comets. Collisions between such bodies produce small dust particles, the spectral features of which reveal their composition and, hence, that of their parent bodies. A measurement of the composition of olivine crystals (Mg(2-2x)Fe(2x)SiO(4)) has been done for the protoplanetary disk HD 100546 (refs 3, 4) and for olivine crystals in the warm inner parts of planetary systems. The latter compares well with the iron-rich olivine in asteroids (x ≈ 0.29). In the cold outskirts of the β Pictoris system, an analogue to the young Solar System, olivine crystals were detected but their composition remained undetermined, leaving unknown how the composition of the bulk of Solar System cometary olivine grains compares with that of extrasolar comets. Here we report the detection of the 69-micrometre-wavelength band of olivine crystals in the spectrum of β Pictoris. Because the disk is optically thin, we can associate the crystals with an extrasolar proto-Kuiper belt a distance of 15-45 astronomical units from the star (one astronomical unit is the Sun-Earth distance), determine their magnesium-rich composition (x = 0.01 ± 0.001) and show that they make up 3.6 ± 1.0 per cent of the total dust mass. These values are strikingly similar to those for the dust emitted by the most primitive comets in the Solar System, even though β Pictoris is more massive and more luminous and has a different planetary system architecture. PMID:23038467

  9. Peridotite hosted chromite, magnesite and olivine deposits of West Anatolia: A review

    NASA Astrophysics Data System (ADS)

    Zedef, Veysel

    2016-04-01

    Turkey has important chromite, magnesite and olivine deposits within peridotite host rocks. The peridotites (harzburgite, verlite, lherzolite and dunite) are mostly serpentinised as a result of metasomatic reaction of olivine and pyroxene minerals with percolating water. The serpentinites are generally an important part of ophiolitic complexes which displays a discontinuous belts all over the country. The chromite deposits are often related to cumulates and tectonites (as Alpine and/or podiform type deposits) and despite their small reserves, their grade can reach up to 58 %. In most deposits, a little enrichment efforts, the grade of chromite can easily be reached from 25 % to 40-45 %. The magnesite deposits of West Anatolia is especially concentrated in three provinces. These provinces are Konya, Kutahya and Eskisehir. The magnesites are of cryptocrystalline type and, like chromite deposits, their reserve are small but have high grade with low FeO-CaO and high MgO ratio. Once again, these deposits are found within serpentinised peridotites of ultramafic belts. The total (proven and inferred) magnesite reserves are approximately 200 million tons, and these are mostly cryptocrystalline character. A small amount of sedimentary magnesite deposits also present in Denizli (SW Anatolia) and Erzincan (Eastern Anatolia). The olivine deposits are found within peridotites of Western Anatolia. Especially, the Kızıldag olivine deposits (located between the border of Antalya and Konya provinces) are noteworthy with its huge (9 billion tons) reserves. The main olivine mineral is forsterite (Mg2SiO4) which has economically important when compared to other olivine mineral fayalite. The deposits have no quality problem but have a serious disadvantages since its location far from the ports and railway stations.

  10. Diffusive modification of primary zoning in olivine cores in Angrite LEW 87051. [Abstract only

    NASA Technical Reports Server (NTRS)

    Mikouchi, T.; Mckay, G.; Miyamoto, M.; Takeda, H.

    1994-01-01

    Angrite LEW 87051 consists of large olivine crystals set in a fine-grained groundmass that clearly represents a crystallized melt. A few olivines contain Ca-poor, Cr-rich cores that crystallized from a very different melt than the outer part of the crystals constituting the majority of olivine in LEW 87051. We evaluate a model in which the cores formed through fractional crystallization of one melt, then were incorporated into a different melt as xenocrysts, whereupon the original zoning patterns were modified by diffusion. Using a similar approach, we calculate zoning patterns for the cores that would result from perfect fractional crystallization, compare them with the observed zoning, and determine whether the differences could result from diffusive modification consistent with known diffusion rates for Ca, Mn, and Cr. Using distribution coefficients from the 1400 C, IW + 1 experiments, we computed CaO, Cr2O3, and MnO abundances in the hypothetical parent melt by inverting the olivine at the centers of the cores. We further assumed that the primary zoning profile for CaO is essentially unmodified, because the diffusion rate of Ca in olivine is slow. We carried out the fractional crystallization calculation until the calculated Ca content was that observed at break in zoning profiles at the outer edge of the core. We then normalized the distance of this calculated profile to the length of the observed profile in the olivine core and calculated profiles for MnO and Cr2O3. The CaO zoning profile agrees well with the observed profile. The observed MnO profile is slightly higher than the calculated profile near the edge. Diffusion calculations indicate that reversal of the general trend of primary zoning through diffusion would require that diffusion of Cr is 5-10x faster than that of Mn.

  11. Effect of Iron Content on the High-Pressure Plasticity of Olivine

    NASA Astrophysics Data System (ADS)

    Holyoke, C. W., III; Raterron, P.; Hilairet, N.; Merkel, S.

    2015-12-01

    The mantle of terrestrial planets are olivine-rich, with Fe/(Mg+Fe) ratio lower than ~2% for Mercury and up to 25-30% for Mars, with intermediate compositions for the Earth, the Moon and Venus. The range of iron contents may promote a range of mantle viscosities, with implications for planet thermal history and surface structures. Indeed, experiments at low pressure (i.e. at 300 MPa, Zhao et al., 2009, EPSL, 287,229-240) indicate that Fe dramatically decreases olivine viscosity. Thus, the Martian mantle may be ~10 times less viscous than the Earth's at the same conditions. However, there is no data available on the effect of iron on olivine plasticity at pressures relevant to planetary interiors. In this study, we deformed polycrystalline olivine specimens with iron ratios of 0%, 10%, 70%, 90% and 100%, at high pressure (P) ranging from 2 to 5 GPa and temperatures (T) in the range 800°-1200°C. Experiments were carried out in the Deformation-DIA apparatus (D-DIA) coupled with x-ray synchrotron radiation - to quantify stress and strain by in-situ diffraction and imaging - at the NSLS (Upton, NY) and the ESRF (Grenoble, France). Stacked cylinders of olivine with different compositions were deformed at steady-state conditions to compare their plastic responses while experiencing identical T, P and differential stresses. Results of these experiments indicate that the weakening effect of Fe on olivine viscosity is not as great at high pressure as the effect observed at low pressure.

  12. Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

    NASA Technical Reports Server (NTRS)

    Niles, Paul B.; Golden, D. C.; Michalski, J.

    2013-01-01

    High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide-spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa-like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars-like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above -40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial

  13. Olivine Weathering and Sulfate Formation Under Cryogenic Conditions

    NASA Astrophysics Data System (ADS)

    Niles, P. B.; Golden, D. C.; Michalski, J. R.

    2013-12-01

    High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide-spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa-like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0°C in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars-like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above -40°C. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfur

  14. Short- and long-term olivine weathering in Svalbard: implications for Mars.

    PubMed

    Hausrath, E M; Treiman, A H; Vicenzi, E; Bish, D L; Blake, D; Sarrazin, P; Hoehler, T; Midtkandal, I; Steele, A; Brantley, S L

    2008-12-01

    Liquid water is essential to life as we know it on Earth; therefore, the search for water on Mars is a critical component of the search for life. Olivine, a mineral identified as present on Mars, has been proposed as an indicator of the duration and characteristics of water because it dissolves quickly, particularly under low-pH conditions. The duration of olivine persistence relative to glass under conditions of aqueous alteration reflects the pH and temperature of the reacting fluids. In this paper, we investigate the utility of 3 methodologies to detect silicate weathering in a Mars analog environment (Sverrefjell volcano, Svalbard). CheMin, a miniature X-ray diffraction instrument developed for flight on NASA's upcoming Mars Science Laboratory, was deployed on Svalbard and was successful in detecting olivine and weathering products. The persistence of olivine and glass in Svalbard rocks was also investigated via laboratory observations of weathered hand samples as well as an in situ burial experiment. Observations of hand samples are consistent with the inference that olivine persists longer than glass at near-zero temperatures in the presence of solutions at pH approximately 7-9 on Svalbard, whereas in hydrothermally altered zones, glass has persisted longer than olivine in the presence of fluids at similar pH at approximately 50 degrees C. Analysis of the surfaces of olivine and glass samples, which were buried on Sverrefjell for 1 year and then retrieved, documented only minor incipient weathering, though these results suggest the importance of biological impacts. The 3 types of observations (CheMin, laboratory observations of hand samples, burial experiments) of weathering of olivine and glass at Svalbard show promise for interpretation of weathering on Mars. Furthermore, the weathering relationships observed on Svalbard are consistent with laboratory-measured dissolution rates, which suggests that relative mineral dissolution rates in the laboratory, in

  15. Reaction-induced fracturing during olivine serpentinization: A mechanistic investigation at the interface scale

    NASA Astrophysics Data System (ADS)

    Plümper, O.; Røyne, A.; Malthe-Sørenssen, A.; King, H. E.; Jamtveit, B.

    2012-04-01

    Serpentinization of the Earth's impermeable upper mantle is one of the most fundamental metamorphic hydration reactions. It governs lithospheric weakening, geochemical subduction zone input and possibly even the formation of life-essential building blocks. Serpentinization relies on fluid pathway generation due to low initial permeability and the large positive solid volume change associated with hydration. Although these pathways can be produced as a tectonic stress response, there is substantial evidence that the volume increase during olivine serpentinization itself generates stresses sufficient to fracture the rock. Nonetheless, the actual fracturing mechanism during olivine serpentinization is largely unexplored. Unconstrained batch experiments (Okamoto et al. 2011, this study) produce comparable hierachial fracture patterns to those found in natural samples demonstrating that no external forces (e.g., tensile stress) are required for fracturing to take place. Combining this with the observation that fluid-mediated mineral replacement advances via an interface-coupled dissolution-reprecipitation mechanism (e.g., Putnis 2009) without solid-state diffusion into the dissolving mineral indicates that classical (stress) corrosion cracking mechanisms cannot describe fracturing during olivine serpentinization. By uniting micro- and nanostructural characteristics ubiquitous to serpentinized olivine grains with a coupled diffusion-reaction-deformation model and crack growth theory this study explores the sub-critical fracturing mechanism at the interfacial scale. We present a new multistep reaction process and test the feasibility of a molecular wedge-assisted fracturing mechanism based on the following ubiquitously identified features: (1) no rotation of grain domains during fragmentation, (2) isotropic fracture orientation distribution with a uniform average width of individual finite length serpentine veins, (3) cumulative fragment area distribution with a log

  16. Experimental shock metamorphism of mono- and polycrystalline olivine - A comparative study

    NASA Technical Reports Server (NTRS)

    Bauer, J. F.

    1979-01-01

    The paper reports on a series of controlled shock recovery experiments which have been performed on over 40 samples including monocrystalline, polycrystalline, dunite, and porous particulate olivine-bearing targets. Results of the mineralogical and petrological analyses of these samples are used to establish a general and comparative diagnosis of shock effects generated in various olivine-bearing materials. Finally, some experiments are conducted under different ambient pO2 conditions so that information on the distribution of observed impact features is derived as a function not only of peak pressure and texture of the target sample, but also of specific environmental conditions.

  17. Olivine Composition of the Mars Trojan 5261 Eureka: Spitzer IRS Data

    NASA Technical Reports Server (NTRS)

    Lim, L. F.; Burt, B. J.; Emery, J. P.; Mueller, M.; Rivkin, A. S.; Trilling, D.

    2011-01-01

    The largest Mars trojan, 5261 Eureka, is one of two prototype "Sa" asteroids in the Bus-Demeo taxonomy. Analysis of its visible/near-IR spectrum led to the conclusion that it might represent either an angritic analog or an olivine-rich composition such as an R chondrite. Spitzer IRS data (5-30 micrometers) have enabled us to resolve this ambiguity. The thermal-IR spectrum exhibits strong olivine reststrahlen features consistent with a composition of approximately equals Fo60-70. Laboratory spectra of R chondrites, brachinites, and chassignites are dominated by similar features.

  18. Phosphoran pyroxene and olivine in silicate inclusions in natural iron-carbon alloy, Disko Island, Greenland

    NASA Technical Reports Server (NTRS)

    Goodrich, C. A.

    1984-01-01

    A survey of literature data on the P contents of olivine, pyroxene, and garnet in mantle xenoliths and the bulk P contents of mantle xenoliths shows that available data is ambiguous as to whether mantle P is primarily contained in silicates or in phosphates, even though phosphates are rarely observed in mantle xenoliths. Garnet probably contains more of the mantle's P than olivine or pyroxene. Bulk P contents of mantle xenoliths vary significantly. Estimation of the primitive mantle P content from xenoliths requires interpretation of the partial melting and contamination histories of the xenoliths.

  19. Natural olivine crystal-fabrics in the western Pacific convergent region

    NASA Astrophysics Data System (ADS)

    Michibayashi, K.

    2015-12-01

    Crystallographic preferred orientations (CPOs) within a natural peridotite commonly consist three pole figures for [100], [010] and [001] axes and are categorized into the well-known five olivine fabric types: A, B, C, D and E, which are easily connected with olivine slip systems: A as (010)[100], B as (010)[001], C as (001)[001], D as {0kl}[100] and E as (001)[100]. The five fabric types have been discussed on flow stress, water contents and pressure effect in mantle. In addition, AG type has also been proposed in recognition of its common occurrence in nature. The development of AG-type is not clear and could require some factors such as complex slip systems, non-coaxial strain types or the effect of melt during plastic flow. Here, we present our olivine fabric database mainly for the convergent margin in the western Pacific region. We introduce a new index named fabric-index angle (FIA) related to P-wave property of a single olivine crystal instead of a tentative classification of CPOs into the six fabric types, so that a set of CPOs can be expressed as a single angle in a range between -90° and 180°. The six olivine fabric types can have unique FIA: 63° for A type, -28° for B type, 158° for C type, 90° for D type, 106° for E type and 0° for AG type. We divided our olivine database into five tectonic groups: ophiolites, ridge peridotites, trench peridotites, peridotite xenoliths and peridotites enclosed in high-pressure metamorphic rocks. Our result shows that although our database is not yet large enough except the trench peridotites to define the characteristic of the five tectonic groups, the natural olivine fabrics vary in a range of the FIA: 0° to 150° for the ophiolites, 40° to 80° for the ridge peridotites, -40° to 100° for the trench peridotites, 0° to 100° for the peridotite xenoliths and -40° to 10° for the peridotites enclosed in high-pressure metamorphic rocks. The trench peridotites show statistically bimodal distribution of FIA

  20. First finding of burkeite in melt inclusions in olivine from sheared lherzolite xenoliths.

    PubMed

    Korsakov, Andrey V; Golovin, Alexander V; De Gussem, Kris; Sharygin, Igor S; Vandenabeele, Peter

    2009-08-01

    For the first time burkeite was observed as a daughter phase in the melt inclusions in olivine by Raman spectroscopy. The olivine comes from sheared lherzolite xenoliths from the Udachnaya-East kimberlite pipe (Yakutia, Russia). This anhydrous sulfate-carbonate mineral (Na(6)(CO(3))(SO(4))(2)) is generally considered to be a characteristic mineral in saline soils or in continental lacustrine evaporite deposits. Recently, however, this mineral was identified in hydrothermal fluids. Our observations indicate that burkeite can also be formed from a mantle-derived melt.

  1. Seismic evidence for olivine phase changes at the 410- and 660-kilometer discontinuities.

    PubMed

    Lebedev, Sergei; Chevrot, Sébastien; van der Hilst, Rob D

    2002-05-17

    The view that the seismic discontinuities bounding the mantle transition zone at 410- and 660-kilometer depths are caused by isochemical phase transformations of the olivine structure is debated. Combining converted-wave measurements in East Asia and Australia with seismic velocities from regional tomography studies, we observe a correlation of the thickness of, and wavespeed variations within, the transition zone that is consistent with olivine structural transformations. Moreover, the seismologically inferred Clapeyron slopes are in agreement with the mineralogical Clapeyron slopes of the (Mg,Fe)2SiO4 spinel and postspinel transformations. PMID:12016311

  2. Dynamic crystallization of chondrule melts of porphyritic olivine composition - Textures experimental and natural

    NASA Technical Reports Server (NTRS)

    Lofgren, Gary

    1989-01-01

    A full range of textures characteristic for porphyritic olivine chondrules was reproduced in melts of the same composition, crystallized under dynamic crystallization conditions (under controlled cooling), as determined by electron microprobe analyses. The primary differences between the natural and experimentally produced porphyritic olivine textures were the nature and the extent of matrix crystallization, which reflected the subsolidus or low-temperature cooling history. The most confining limits on the chondrule-forming process were found to be the presence of crystalline precursors for the chondrule melts and the upper temperature limit of melting.

  3. Dehydration breakdown of antigorite and the formation of B-type olivine CPO

    NASA Astrophysics Data System (ADS)

    Nagaya, Takayoshi; Wallis, Simon R.; Kobayashi, Hiroaki; Michibayashi, Katsuyoshi; Mizukami, Tomoyuki; Seto, Yusuke; Miyake, Akira; Matsumoto, Megumi

    2014-02-01

    Peridotite formed by contact metamorphism and dehydration breakdown of an antigorite schist from the Happo area, central Japan shows a strong olivine crystallographic preferred orientation (Ol CPO). The lack of mesoscale deformation structures associated with the intrusion and the lack of microstructural evidence for plastic deformation of neoblastic grains suggest that olivine CPO in this area did not form as a result of solid-state deformation. Instead, the good correspondence between the original antigorite orientation and the orientation of the newly formed olivine implies the CPO formed by topotactic growth of the olivine after antigorite. Ol CPO is likely to develop by a similar process in subduction zone environments where foliated serpentinite is dragged down to depths where antigorite is no longer stable. The Happo Ol CPO has a strong a-axis concentration perpendicular to the lineation and within the foliation-commonly referred to as B-type Ol CPO. Seismic fast directions parallel to the ocean trench are observed in many convergent margins and are consistent with the presence of B-type Ol CPO in the mantle wedge of these regions. Experimental work has shown that B-type CPO can form by dislocation creep under hydrous conditions at relatively high stresses. There are, however, several discrepancies between the characteristics of natural and laboratory samples with B-type Ol CPO. (1) The formation conditions (stress and temperature) of some natural examples with B-type CPO fall outside those predicted by experiments. (2) In deformation experiments, slip in the crystallographic c-axis direction is important but has not been observed in natural examples of B-type CPO. (3) Experimental work suggests the presence of H2O and either high shear stress or relatively low temperatures are essential for the formation of B-type CPO. These conditions are most likely to be achieved close to subduction boundaries, but these regions are also associated with serpentinization

  4. The olivine-ilmenite thermometer. [partitioning effect of temperature on iron ions and magnesium

    NASA Technical Reports Server (NTRS)

    Andersen, D. J.; Lindsley, D. H.

    1979-01-01

    It is noted that the partitioning of Fe(2+) and Mg between olivine and ilmenite is temperature-dependent and can serve as a geothermometer if the activity-composition relations are determined. The paper reports on the study of the partitioning from 700-980 C at 1 kbar and 800-900 C at 13 kbar, and develops a solution model to account for the nonideality of olivine in the binary system fosterite-fayalite and for ilmenite in the ternary system ilmenite-geikielite-hematite. A comparison with crystallization experiments shows that this thermometer may be safely extrapolated to temperatures higher than those of the exchange experiments.

  5. First finding of burkeite in melt inclusions in olivine from sheared lherzolite xenoliths.

    PubMed

    Korsakov, Andrey V; Golovin, Alexander V; De Gussem, Kris; Sharygin, Igor S; Vandenabeele, Peter

    2009-08-01

    For the first time burkeite was observed as a daughter phase in the melt inclusions in olivine by Raman spectroscopy. The olivine comes from sheared lherzolite xenoliths from the Udachnaya-East kimberlite pipe (Yakutia, Russia). This anhydrous sulfate-carbonate mineral (Na(6)(CO(3))(SO(4))(2)) is generally considered to be a characteristic mineral in saline soils or in continental lacustrine evaporite deposits. Recently, however, this mineral was identified in hydrothermal fluids. Our observations indicate that burkeite can also be formed from a mantle-derived melt. PMID:19058996

  6. Space Weathering of Olivine in Lunar Soils: A Comparison to Itokawa Regolith Samples

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Berger, E. L.

    2014-01-01

    Regolith particles from airless bodies preserve a record of the space weathering processes that occurred during their surface exposure history. These processes have major implications for interpreting remote-sensing data from airless bodies. Solar wind irradiation effects occur in the rims of exposed grains, and impact processes result in the accumulation of vapordeposited elements and other surface-adhering materials. The grains returned from the surface of Itokawa by the Hayabusa mission allow the space weathering "style" of a chondritic, asteroidal "soil" to be compared to the lunar case. Here, we present new studies of space-weathered olivine grains from lunar soils, and compare these results to olivine grains from Itokawa. Samples and Methods: We analyzed microtome thin sections of olivine grains from the 20-45 micron fractions of three lunar soils: 71061, 71501 and 10084 (immature, submature and mature, respectively). Imaging and analytical data were obtained using a JEOL 2500SE 200kV field-emission scanning-transmission electron microscope equipped with a thin-window energy-dispersive x-ray spectrometer. Similar analyses were obtained from three Hayabusa olivine grains. Results and Discussion: We observed lunar grains showing a range of solar flare track densities (from <10(exp 9) to approx.10(exp 12)/sq cm). The lunar olivines all show disordered, highly strained, nanocrystalline rims up to 150-nm thick. The disordered rim thickness is positively correlated with solar flare track density. All of the disordered rims are overlain by a Si-rich amorphous layer, ranging up to 50-nm thick, enriched in elements that are not derived from the host olivine (e.g., Ca, Al, and Ti). The outmost layer represents impact-generated vapor deposits typically observed on other lunar soil grains. The Hayabusa olivine grains show track densities <10(exp 10)/sq cm and display disordered rims 50- to 100-nm thick. The track densities are intermediate to those observed in olivines

  7. A valid Margules formulation for an asymmetric ternary solution - Revision of the olivine-ilmenite thermometer, with applications

    NASA Technical Reports Server (NTRS)

    Andersen, D. J.; Lindsley, D. H.

    1981-01-01

    A derivation of a valid asymmetric ternary Margules expression for the excess free energy is presented, and the olivine-ilmenite thermometer is revised accordingly. Although the effect on the thermometer is relatively small, the revision results in improved precision. Estimated temperatures of equilibration are presented for olivine and ilmenite from lunar and terrestrial rocks.

  8. Reduced chromium in olivine grains from lunar basalt 15555 - X-ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Jones, K. W.; Gordon, B.; Rivers, M. L.; Bajt, S.; Smith, J. V.

    1993-01-01

    The oxidation state of Cr in 200-micron regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results, coupled with the apparent f(02)-independence of partitioning coefficients for Cr into olivine, imply that the source magma was dominated by divalent Cr at the time of olivine crystallization.

  9. Aqueous corrosion of olivine in the Mars meteorite Miller Range (MIL) 03346 during Antarctic weathering: Implications for water on Mars

    NASA Astrophysics Data System (ADS)

    Velbel, Michael A.

    2016-05-01

    Several nakhlites (clinopyroxenite meteorites from Mars) contain olivine phenocrysts with corrosion features identical in size, shape and distribution to the smaller etch-pits of well-characterized weathered terrestrial olivine. Miller Range (MIL) 03346 is an Antarctic nakhlite find, recovered after long exposure to Antarctic conditions. The distribution of discrete olivine etch-pits almost exclusively within a few hundred microns of allocation MIL 03346,171's documentably exposed surface suggests that they formed by terrestrial weathering in Antarctica. The small size of olivine etch-pits in MIL 03346,171 relative to commonly much larger etch-pits in even incipiently weathered terrestrial examples suggests that the duration of its exposure to weathering conditions was short, or the weathering conditions to which it was exposed did not favor olivine corrosion (in the form of etch-pit formation), or both. Time-scales for the formation of etch-pits, estimated from experimentally determined dissolution rates of olivine over a range of pHs, are comparable to the measured terrestrial age of the meteorite and short relative to the time available for possible similar corrosion on Mars. Etch-pits of the observed size on MIL 03346 olivine phenocrysts would be relatively easy to form supraglacially under brief episodic acidic Antarctic conditions, but the terrestrial age of MIL 03346 is long enough that its olivine might have been weathered to the observed state by englacial films of alkaline Antarctic water. The paucity of similar etch-pits in olivine from the interior of MIL 03346 suggests that olivine in this Mars meteorite was exposed to even less aqueous alteration after iddingsitization during its 1.3 billion years on Mars than its exterior was subjected to during its Pleistocene-Holocene exposure to Antarctic weathering conditions.

  10. Chlorine/Bromine Ratios in Fracture-filling Aqueous Alteration Products in Nakhla Olivine

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Rao, M. N.; Dreibus, G.; McKay, D. S.; Waenke, H.; Wentworth, S.; Newville, M.; Trainor, T.; Flynn, G. J.

    2002-01-01

    The Cl/Br ratios in fracture-filling materials in veins in Nakhla olivine was determined using x-ray microprobe (Br) and EDX (Cl) techniques. The Cl/Br ratio of 55 (standard deviation: 13) shows that the secondary altered material is pristine, extraterrestrial and akin to the Martian soil. Additional information is contained in the original extended abstract.

  11. Pyroxenes and olivines: Structural implications of shock-wave data for high pressure phases

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.; Ahrens, T. J.

    1975-01-01

    The nature of the shock-induced, high-pressure phases of olivine and pyroxene rocks is examined in the light of data for the densities of a new class of perovskite-related silicate structures. Also examined are some new Hugoniot and release adiabat data for bronzite. Reexamining available shock data for magnesian pyroxenes and olivines leads to the conclusion that they define a mixed phase (or disequilibrium) region to about the 100 GPa range, related to the kinetics of phase transformation in these silicates. By recognizing this point, certain discrepancies in previous interpretations of shock data can be explained. A set of theoretical Hugonoits for pyroxene and olivine stoichiometry, perovskite-bearing assemblages was constructed based on their properties deduced from high-pressure work, showing that the shock data is compatible with transformations to perovskites in the 45-7GPa region. Finally, the shock data indicate very similar properties for olivine and pyroxene at high pressures making them both equally likely candidates for the lower mantle.

  12. Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-07-01

    We report the B abundances and isotopic ratios of two olivine grains from the S-type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in 10B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and 11B/10B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic-ray spallation reactions) rich in 10B. This observation is consistent with the short cosmic-ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic 21Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in 10B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.

  13. Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-09-01

    We report the B abundances and isotopic ratios of two olivine grains from the S-type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in 10B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and 11B/10B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic-ray spallation reactions) rich in 10B. This observation is consistent with the short cosmic-ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic 21Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in 10B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.

  14. The fate of fluid inclusions during high-temperature experimental deformation of olivine aggregates

    NASA Astrophysics Data System (ADS)

    Carter, Matthew J.; Zimmerman, Mark E.; Teyssier, Christian

    2015-05-01

    Torsion experiments on initially wet and dry olivine aggregates at equivalent deformation conditions investigated the fate of fluid inclusions (FIs) during high-temperature deformation. Wet samples were produced by adding water to San Carlos olivine powders before hot pressing; those hot pressed without water are considered dry. After hot pressing, wet and dry aggregates have comparable grain sizes, but wet aggregates have more abundant primary FIs. Talc jackets were fitted around some wet and dry samples prior to deformation to hydrate samples during deformation via talc dehydration at elevated temperature, whereas other samples were deformed without talc. At similar strain rates (~1.0 × 10-4 s-1), the peak shear stress for the dry sample (no talc) was 190-220 MPa, whereas all other samples reached 180 MPa; the strengths of wet (± talc) and dry (+ talc) specimens appear similar. Deformed samples reveal abundant FIs, reduced grain size, shape preferred orientation of olivine, and a pervasive low-angle fabric (C') to the shear plane defined by aligned FIs. Samples deformed with talc have FI-rich and FI-depleted domains; where FIs are abundant, the C' fabric is better developed and grain size is smaller. Electron backscatter diffraction pole figures suggest that olivine deformed in the dislocation creep regime via the (010)[100] slip system. Results of these experiments suggest that FIs are redistributed during dislocation creep, leading to the development of grain-scale, high-diffusivity pathways.

  15. Temperature dependence of [100](010) and [001](010) dislocation mobility in natural olivine

    NASA Astrophysics Data System (ADS)

    Wang, Lin; Blaha, Stephan; Pintér, Zsanett; Farla, Robert; Kawazoe, Takaaki; Miyajima, Nobuyoshi; Michibayashi, Katsuyoshi; Katsura, Tomoo

    2016-05-01

    Dislocation recovery experiments were conducted on pre-deformed olivine single crystals at 1450 to 1760 K, room pressure, and oxygen partial pressures near the Ni-NiO buffer to determine the annihilation rates for [100] and [001] dislocations on the (010) plane. Olivine single crystals were first deformed to activate the desired slip systems under simple shear geometry and then annealed at target conditions. The edge and screw dislocations with Burgers vectors, b, of [100] and [001], respectively, both elongated in the [001] direction were produced by the deformation. The dislocation annihilation rate constants of both types of dislocations are identical within 0.3 log unit. The activation energies for both dislocations are also identical, i.e., ∼400 kJ/mol, which is also identical to that of the Si self-diffusion coefficient. This correspondence suggests that olivine dislocation creep controlled by a diffusion-controlled process under low-stress and high-temperature conditions. This study offers a potential insight into the formation of AG-type fabric in olivine.

  16. In situ Ultrasonic Velocity Measurements Across the Olivine-spinel Transformation in Fe2Si04

    SciTech Connect

    Liu, Q.; Liu, W; Whitaker, M; Wang, L; Li, B

    2010-01-01

    Compressional (P) and shear (S) wave velocities across the olivine-spinel transformation in Fe{sub 2}SiO{sub 4} were investigated in situ using combined synchrotron X-ray diffraction, X-ray imaging, and ultrasonic interferometry up to 5.5 GPa along the 1173 K isotherm. The onset of the spinel to olivine transformation at 4.5 GPa and olivine to spinel transition for Fe{sub 2}SiO{sub 4} at 4.8 GPa was concurrently observed from X-ray diffraction, the amplitude of the ultrasonic signals, the calculated velocities, and the ratio of P and S wave velocities (v{sub P}/v{sub S}). No velocity softening was observed prior to the fayalite to spinel transition. The velocity contrasts across the Fe{sub 2}SiO{sub 4} spinel to fayalite phase transition are derived directly from the measured velocities, which are 13 and 12% for P and S waves, respectively, together with a density contrast of 9.4%. A comparison with literature data indicates that the changes in compressional-wave velocity and density across the olivine-spinel transformation in Fe{sub 2}SiO{sub 4} are comparable to those with different iron concentrations in the (Mg,Fe){sub 2}SiO{sub 4} solid solution, whereas the shear wave velocity contrast decreases slightly with increasing iron concentration.

  17. Origin and mineralogy of olivine-dominated near-Earth Asteroids

    NASA Astrophysics Data System (ADS)

    Burt, Brian J.; DeMeo, Francesca E.; Binzel, Richard P.

    2014-06-01

    Dynamical lifetimes of near-Earth asteroids (NEAs) are shorter than the age of the Solar System thus necessitating resupply from the Main Belt. The NEA population, because of its proximity, allows us to explore asteroids at a size-range not possible among asteroids further away in the Main Belt. There are very few olivine-dominated asteroids, identified as spectroscopic A-types (Bus & Binzel 2002, DeMeo et al. 2009), among the near-Earth population (Binzel et al. 2004). While a number of NEAs were labeled olivine-rich from visible wavelength data, near-infrared observations of these objects prove the olivine-rich population is exceedingly rare. We identify (1951) Lick, (5261) Eureka, and a new third A-type object, (5131) 1990 BG. Using a radiative transfer model (Shkuratov et al. 1999) and band parameter analysis we mineralogically characterize and compare these three olivine-rich A-type asteroids. Additionally, using the model from Bottke et al. 2002, we present main-belt source regions for these bodies. Finally, we compare these NEA A-types to the main belt A-type population.

  18. Methodology of Space Weathering Simulation and Its Application on Olivine and Pyroxene Samples

    NASA Astrophysics Data System (ADS)

    Malina, Ondrej; Kohout, Tomas; Tucek, Jiri; Filip, Jan; Britt, Daniel; Zboril, Radek

    2015-11-01

    Here, we reported a two-step thermal treatment method [1] for the space weathering simulation and the differences in the formation of metallic iron nanoparticles (npFe0) on the surface of olivine and pyroxene samples are discussed.In general, the main goal is in controlled size of npFe0 formed on the surface of olivine and pyroxene and in quantification of the related spectral changes. The transmission electron microscopy (TEM) after double-heating method revealed two significant features. First, different sizes and concentration of npFe0 are observed, and secondly, due to more resistance of pyroxene (e.g. [2]), higher temperatures are needed to produce the same amount of npFe0 as in the olivine case. [1]Results from TEM are fully consistent with reflectance spectra, which show progressive changes as a function of the increasing npFe0 amount. The reason for the observed differences in reflectance spectra can be found in the crystal structure and local environment at each crystallographic position of both samples. It is very similar as in the case of laser heating experiments (e.g. [2]), where the surface of orthopyroxene is significantly more resistant to reduction than olivine due to mobility of oxygen and cation diffusions from the bulk to surface of the samples.References:[1] Kohout T. et al. (2014) Icarus, 237, 75-83[2] Quadery A. et al (2015) JGR-Planets 120, 1-19.

  19. Spinel from Apollo 12 Olivine Mare Basalts: Chemical Systematics of Selected Major, Minor, and Trace Elements

    NASA Technical Reports Server (NTRS)

    Papike, J. J.; Karner, J. M.; Shearer, C. K.; Spilde, M. N.

    2002-01-01

    Spinels from Apollo 12 Olivine basalts have been studied by Electron and Ion microprobe techniques. The zoning trends of major, minor and trace elements provide new insights into the conditions under which planetary basalts form. Additional information is contained in the original extended abstract.

  20. Compositional Variations of Olivines and Pyroxenes in Chondritic Interplanetary Dust Particles

    NASA Astrophysics Data System (ADS)

    Zolensky, M.; Barrett, R.

    1992-07-01

    It is a fundamental goal of interplanetary dust particle (IDP) research to determine the sources and histories of these primitive extraterrestrial materials. Chondritic IDPs have been divided into anhydrous and hydrous varieties. The presumption is that hydrated IDPs experienced aqueous alteration on parent bodies (hydrous asteroids or possibly comets). We wish to discover whether the anhydrous IDPs were the initial raw materials for these reactions. We report here analyses of olivines and pyroxenes from 22 large (>15 micrometers) chondritic IDPs: 11 anhydrous and 11 hydrous. We find there exists no significant difference in the compositions of olivines from olivine vs. pyroxene dominated IDPs. The degree of heterogeneity of these olivine compositions from anhydrous IDPs (Fo44-100) is great, significantly exceeding that of the olivines from the hydrous IDPs (Fo76-100) we examined. We observe the same relationship for orthopyroxenes (En57-100 for anhydrous, En79-100 for hydrous). Interestingly, we encountered true diopsides predominantly in pyroxene-dominated hydrous IDPs. Some anhydrous IDPs also displayed restricted compositional ranges for olivines and pyroxenes. For sulfate- containing anhydrous IDPs, olivines and orthopyroxenes had the ranges Fo91-100 and En94-100; for melted (atmospherically ablated) IDPs these ranges were Fo90-100 and En91-94. Are hydrous and anhydrous IDPs genetically related? With the exception of some from the serpentine class (Bradley and Brownlee, 1991), all chondritic IDPs have nearly identical mineralogies (Zolensky and Lindstrom, 1992). The compositional ranges of olivines and pyroxenes in these materials are quite dissimilar, with those from hydrous IDPs being relatively magnesium-rich; however this could be explained by a relatively greater ease of destruction of iron-rich silicates during aqueous alteration. It is known that increasing the Fe^2+ content of olivine decreases the temperature at which serpentinization occurs (Deer et

  1. Elasticity of single-crystal olivine at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Mao, Zhu; Fan, Dawei; Lin, Jung-Fu; Yang, Jing; Tkachev, Sergey N.; Zhuravlev, Kirill; Prakapenka, Vitali B.

    2015-09-01

    Elasticity of single-crystal San Carlos olivine has been derived from sound velocity and density measurements at simultaneous high pressure-temperature conditions up to 20 GPa and 900 K using in situ Brillouin spectroscopy and single-crystal X-ray diffraction in externally-heated diamond anvil cells. These experimental results are used to evaluate the combined effect of pressure and temperature on full elastic constants of single-crystal olivine to better understand its velocity profiles and anisotropies in the deep mantle. Analysis of the results shows that the shear moduli display strong concave behaviors as a function of pressure at a given high temperature, while the longitudinal modulus, C11, and the off-diagonal moduli, C12 and C13, exhibit greater temperature dependence at higher pressures than at relatively lower pressures. Using a finite-strain theory and thermal equation of state modeling for a pyrolitic mantle composition along an expected mantle geotherm, our results show that the magnitude of the VP and VS jumps at the 410-km depth are 6% and 6.4%, respectively, which are greater than that found in seismic observations, suggesting a mantle olivine content of 40-50 vol%, which is less than what is expected for the pyrolite model. Our modeled velocity profiles for a metastable olivine wedge in the subduction slabs along a representative cold slab geotherm are 6% and 10% lower than those of wadsleyite and ringwoodite, respectively, at corresponding depths of the normal mantle. Our modeled results also show that metastable olivine in the cold slabs could have strong VP and VS anisotropies. The maximum VP anisotropy is estimated to be 19-22% at transition zone depth, whereas the maximum VS splitting is 13-23% and increases with depth. As a result, the presence of a metastable olivine wedge at the transition zone depth would exhibit a seismic signature of low velocity and strong seismic anisotropy which are consistent with recent seismic observations for

  2. Origin of Aristarchus Olivine Deposits Based on M3, WAC, and Diviner Analyses

    NASA Astrophysics Data System (ADS)

    Wiseman, S. M.; Mustard, J. F.; Donaldson Hanna, K. L.; Isaacson, P.; Jolliff, B. L.; Besse, S.; Staid, M.; Pieters, C. M.

    2011-12-01

    The Aristarchus region contains geologically diverse deposits and the Aristarchus impact crater, located on the SE margin of the plateau near the contact between plateau materials and western Procellarum basalts, has exposed materials with variable compositions. Of particular interest is the origin of olivine-bearing deposits that occur on the SE portion of the crater rim and ejecta in association with impact melt [1]. NW portions of the rim and ejecta expose plateau materials and are spectrally dominated by pyroxene in the VNIR. Spectra of the NW rim and ejecta are consistent with a noritic composition and with the inferred origin of the plateau as uplifted upper crust [2,3,4]. Therefore, it is unlikely that the olivine- bearing materials, which exhibit a strong 1 micron olivine absorption and only minor pyroxene contributions, are derived from plateau materials similar to those exposed in the NW portion of the crater. Potential sources of the olivine-bearing material excavated by the impact include western Procellarum basalts or buried material associated with the Marius Hills volcanic complex. Alternatively, the olivine-bearing deposits could be derived from a shallow pluton that is not represented by other surface exposures or could have formed as re-crystallized impact melt. Both the western Procellarum basalts [5,6] and some units associated with the Marius Hills [7] are olivine-bearing. In order to differentiate between these hypotheses, we are integrating spectral data in the UV/VIS (LRO WAC), VIS/NIR (Chandrayaan-1 M3), and TIR (LRO Diviner) to further characterize the assemblages of minerals that occur in association with the olivine-bearing deposits in Aristarchus crater, western Procellarum, and units within the Marius Hills volcanic complex. [1] Mustard et al., 2011, JGR 116. [2] McEwen et al., 1994, Science 266. [3] Lucey et al., 1986, LPSC 16. [4] Chevrel et al., 2009, Icarus 199. [5] Staid and Pieters 2001, JGR. [6] Staid et al., 2011, JGR 116. [7

  3. UNDERSTANDING OLIVINE CO2 MINERAL SEQUESTRATION MECHANISMS AT THE ATOMIC LEVEL: OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    M.J. McKelvy; H. Bearat; A.V.G. Chizmeshya; R. Nunez; R.W. Carpenter

    2003-08-01

    Carbonation of Mg-rich minerals offers an intriguing candidate carbon sequestration process technology, which can provide large-scale CO{sub 2} disposal. Such disposal bypasses many long-term storage problems by (i) providing containment in the form of mineral carbonates that have proven stable over geological time, (ii) generating only environmentally benign materials, and (iii) essentially eliminating the need for continuous site monitoring. The primary challenge for viable process development is reducing process cost. This is the primary focus of the CO{sub 2} Mineral Sequestration Working Group managed by Fossil Energy at DOE, which includes members from the Albany Research Center, Los Alamos National Laboratory, the National Energy Technology Laboratory, Penn State University, Science Applications International Corporation, and the University of Utah, as well as from our research group at Arizona State University. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a leading process candidate, which converts CO{sub 2} into the mineral magnesite (MgCO{sub 3}). As olivine carbonation is exothermic, it offers intriguing low-cost potential. Recent studies at the Albany Research Center have found aqueous-solution carbonation is a promising approach. Cost effectively enhancing carbonation reactivity is central to reducing process cost. Many of the mechanisms that impact reactivity occur at the solid/solution interface. Understanding these mechanisms is central to the ability to engineer new and modified processes to enhance carbonation reactivity and lower cost. Herein, we report the results of our UCR I project, which focused on exploring the reaction mechanisms that govern aqueous-solution olivine carbonation using model olivine feedstock materials. Carbonation was found to be a complex process associated with passivating silica layer formation, which includes the trapping of magnesite nanocrystals within the passivating

  4. Olivine alteration and H2 production in carbonate-rich, low temperature aqueous environments

    NASA Astrophysics Data System (ADS)

    Neubeck, Anna; Duc, Nguyen Thanh; Hellevang, Helge; Oze, Christopher; Bastviken, David; Bacsik, Zoltán; Holm, Nils G.

    2014-06-01

    Hydrous alteration of olivine is capable of producing molecular hydrogen (H2) under a wide variety of hydrothermal conditions. Although olivine hydrolysis (i.e., serpentinization) has commonly been assessed at elevated temperatures (>100 °C), the nature of these reactions in relation to H2 production at lower temperatures has not been systematically evaluated, especially with regard to carbonate-rich fluids. Specifically, carbonate formation may kinetically infringe on geochemical routes related to serpentinization and H2 production at lower temperatures. Here time-dependent interactions of solid, liquid, and gaseous phases with respect to olivine hydrolysis in a carbonate-rich solution (20 mM HCO3-) at 30, 50 and 70 °C for 315 days is investigated experimentally. Within the first two months, amorphous Si-rich (i.e., talc-like) and carbonate phases precipitated; however, no inhibition of olivine dissolution is observed at any temperature based on surface chemistry analyses. High-resolution surface analyses confirm that precipitates grew as spheroids or vertically to form topographic highs allowing further dissolution of the free olivine surfaces and exposing potential catalysts. Despite no magnetite (Fe3O4) being detected, H2 increased with time in experiments carried out at 70 °C, indicating an alternative coupled route for Fe oxidation and H2 production. Spectrophotometry analyses show that aqueous Fe(II) is largely converted to Fe(III) potentially integrating into other phases such as serpentine and talc, thus providing a viable pathway for H2 production. No increase in H2 production was observed in experiments carried out at 30 and 50 °C supporting observations that incorporation of Fe(II) into carbonates occurred faster than the intertwined processes of olivine hydrolysis and Fe(III) oxidation. Overall, carbonate formation is confirmed to be a major influence related to H2 production in low-temperature serpentinization systems. We studied low temperature

  5. Studying the pseudomorphic replacement of olivine by silica at acidic conditions

    NASA Astrophysics Data System (ADS)

    King, Helen E.; Geisler, Thorsten; Putnis, Andrew

    2010-05-01

    Silicification is an important reaction occurring in volcanic environments that aids the neutralisation of the extremely acidic fluids produced. Replacement of the original minerals by silica results in the reacting fluid becoming enriched in cations that can be subsequently transported through the hydrothermal system (Varekamp et al., 2000). In some examples olivine and pyroxene phenocrysts within the reacted layers are pseudomorphically replaced by silica (Africano and Bernard, 2000). We have performed unstirred batch experiments using sulphuric acid and whole olivine crystals to explore the parameters that control phase precipitation and the pseudomorphic replacement of forsteritic olivine. The experiments were conducted in Teflon-lined steel autoclaves at temperatures between 80 and 120 ° C. In lower temperature experiments the reaction of olivine with 0.1 M sulphuric acid produced a red precipitate coating the olivine surface. The red phase was too low in concentration to be identified but is expected to be hematite (Fe2O3). In contrast, experiments conducted in sulphuric acid between 1 and 3.6 M produced an amorphous silica pseudomorph of olivine. The dependence of phase precipitation on pH was tested using a sulphuric acid solution neutralised to pH 2 with a resulting ionic strength equivalent to 1 M. At low temperatures the olivine reacted to produce amorphous silica and a yellow fluid indicating that Fe remained in solution, possibly as a complex with sulphate. Higher temperatures allowed the iron to be liberated from the fluid and precipitated as hematite in association with amorphous silica. Elemental content microprobe data for the olivine and silica rim from pseudomorphic replacement reactions suggests that the majority of cations from olivine dissolution remained in solution. This observation was confirmed by inductively coupled plasma-mass spectroscopy, which showed a high content of Mg and Fe in the fluid. The variation of replacement products at

  6. Development of olivine crystallographic preferred orientation in response to strain-induced fabric geometry

    NASA Astrophysics Data System (ADS)

    Chatzaras, Vasileios; Kruckenberg, Seth C.; Cohen, Shaina M.; Medaris, L. Gordon, Jr.; Withers, Anthony C.; Bagley, Brian

    2016-04-01

    The effect of finite strain ellipsoid geometry on crystallographic preferred orientation (CPO) is well known for crustal minerals (e.g., quartz, calcite, biotite, and hornblende). In the upper mantle, however, it remains poorly constrained how strain and fabric may affect olivine CPO. We present data from a suite of 40 spinel peridotite xenoliths from Marie Byrd Land (west Antarctica), which support an interpretation that fabric geometry rather than deformation conditions control the development of olivine CPO. We use X-ray computed tomography (XRCT) to quantitatively determine spinel fabric (orientation and geometry). Olivine CPOs, determined by Electron Backscattered Diffraction (EBSD), are plotted with respect to the XRCT-derived spinel foliation and lineation; this approach allows for the accurate, and unbiased, identification of CPO symmetries and types in mantle xenoliths. The combined XRCT and EBSD data show that the xenoliths are characterized by a range of fabric geometries (from oblate to prolate) and olivine CPO patterns; we recognize the A-type, axial-[010], axial-[100], and B-type patterns. The mantle xenoliths equilibrated at temperatures 779-1198 oC, as determined by 2-Px geothermometry. Using a geotherm consistent with the stability of spinel in all xenoliths, the range of equilibration temperatures occurs at depths between 39 and 72 km. Olivine recrystallized grain size piezometry reveals differential stresses ranging 2-60 MPa. Analysis of low-angle misorientation axes show a wide range in the distribution of rotation axes, with dominant {0kl}[100] slip. We use Fourier Transform Infrared (FTIR) spectroscopy to estimate the water content in the xenolith with the B-type CPO pattern. FTIR analysis shows that the equilibrium H concentration in olivine is low (4-13 ppm H2O). Combining these data, we observe that olivine CPO symmetry is controlled neither by the deformation conditions (stress, temperature, pressure, water content) for the range of

  7. Diffusivity of hydrogen in iron-bearing olivine at 3 GPa

    NASA Astrophysics Data System (ADS)

    Demouchy, Sylvie; Thoraval, Catherine; Bolfan-Casanova, Nathalie; Manthilake, Geeth

    2016-11-01

    The kinetics of hydrogenation of dry iron-bearing olivine single crystals was determined by performing hydration experiments under hydrothermal conditions at high pressure. The experiments were performed in a multi-anvil press at 3 GPa, for a temperature range between 900 and 1200 °C and for various durations. The oxygen fugacity was buffered along Ni-NiO joint. Polarized Fourier transform infrared spectroscopy and recent empirical calibration were used to quantify the hydroxyl distributions in the samples along crystallographic axes after the experiments. The chemical diffusion coefficients are similar (barely slower) than in olivine hydrated at lower pressure (0.2 and 0.3 GPa) for the same diffusion mechanism. Under the given experimental conditions, the anisotropy of diffusion is the same as for proton-vacancy mechanism, with diffusion along the [0 0 1] axis faster than along the [1 0 0]. However, the anisotropy at 3 GPa is weaker compared to measurements at lower pressures and the analysis of concentration profiles using 3D models shows that an isotropic solution could also be relevant. Fits of the diffusion data to an Arrhenius law yield activation energies for the slightly faster [0 0 1] axis of the crystallographic axes around 198 ± 5 kJ mol-1, a value only slightly lower than the results from previous experimental studies for natural iron-bearing olivine hydrogenated at lower confining pressure. At 3 GPa, hydrogenation can be well approximated by a single mechanism controlled by coupled diffusion of protons and octahedral vacancies (di- and tri-valent ions). The diffusion rates are fast enough to alter hydrogen concentration within olivine in xenoliths ascending from the mantle or experiencing hydrogen-rich metasomatism events, but too slow to permit complete homogenization of hydrogen in olivine-rich rocks at kilometer scale in less than one My.

  8. How do olivines record magmatic events? Insights from major and trace element zoning

    NASA Astrophysics Data System (ADS)

    de Maisonneuve, C. Bouvet; Costa, F.; Huber, C.; Vonlanthen, P.; Bachmann, O.; Dungan, M. A.

    2016-06-01

    Reconciling the diverse records of magmatic events preserved by multiple crystals and minerals in the same sample is often challenging. In the case of basaltic-andesites from Volcán Llaima (Chile), Mg zoning in olivine is always simpler than Ca zoning in plagioclase. A model that explains a number of chemical patterns is that Llaima magmas stall in the upper crust, where they undergo decompression crystallization and form crystal-mush bodies. Frequent magma inputs from deeper reservoirs provide the potential for remobilization and eruption. The records of multiple recharge events in Llaima plagioclase versus an apparent maximum of one such event in coexisting olivine are addressed by using trace element zoning in olivine phenocrysts. We have integrated elements that (1) respond to changes in magma composition due to recharge or mixing (Mg, Fe, Ni, Mn, ±Ca), with (2) elements that are incorporated during rapid, disequilibrium crystal growth (P, Ti, Sc, V, Al). A more complex history is obtained when these elements are evaluated considering their partition coefficients, diffusivities, and crystal growth rates. The olivine archive can then be reconciled with the plagioclase archive of magma reservoir processes. Olivine (and plagioclase) phenocrysts may experience up to three or more recharge events between nucleation and eruption. Diffusion modeling of major and trace element zoning in two dimensions using a new lattice Boltzmann model suggests that recharge events occur on the order of months to a couple of years prior to eruption, whereas crystal residence times are more likely to be on the order of a few years to decades.

  9. Direct Shear of Olivine Single Crystals at the Transition from Asthenospheric to Lithospheric Temperatures

    NASA Astrophysics Data System (ADS)

    Tielke, J. A.; Zimmerman, M. E.; Kohlstedt, D. L.

    2014-12-01

    Models of geodynamic processes require constitutive equations that describe the rheological properties of olivine-rich mantle rocks. An extensive database exists for high-temperature deformation of olivine single crystals and aggregates. However, extrapolation of flow laws derived from high-temperature experiments to temperatures typical of the lithospheric mantle results in significant overestimation of olivine strength. Although some studies have explored the low-temperature deformation of olivine, constitutive equations describing the rheological properties of the four dominate dislocation slip systems over a large range of temperature and stress conditions have yet to be established. To investigate the rheological properties of olivine single crystals deforming by dislocation creep at asthenospheric and lithospheric temperatures, a series of direct shear experiments were carried out. The direct shear geometry permits isolation of the four dominate dislocation slip systems, whereas only two slip systems can be independently activated during triaxial compression. The experiments were carried out in a gas-medium deformation apparatus at temperatures of 1000-1300°C, a confining pressure of 300 MPa, and shear stresses of 81 to 334 MPa that result in shear strain rates of 1.0 x 10-5 to 2.6 x 10-3 s-1. At high-temperature and low-stress conditions, strain rate follows a power law relationship with stress. At low-temperature and high-stress conditions, strain rate depends exponentially on stress. These observations are consistent with a transition from strain rate limited by a climb-controlled dislocation mechanism at higher temperatures to strain rate limited by a glide-controlled dislocation mechanism at lower temperatures.

  10. Some Issues on the Lattice-Preferred Orientation in Olivine-Rich Rocks

    NASA Astrophysics Data System (ADS)

    Karato, S. I.; Mohiuddin, A.; Jiang, Z.; Girard, J.; Xu, H.

    2015-12-01

    During the last several years, various new results were reported on the LPO (lattice-preferred orientation) of olivine that would require major modifications to the paradigms established by the previous studies (for a review see (Karato et al., 2008)). They include (i) the development of strong LPO in the diffusion creep (Miyazaki et al., 2013), (ii) the development of the B-type fabric under dry, low stress torsion deformation at the presence of a small amount of melt (Kohlstedt and Holtzman, 2009) (also Holtzman et al., 2003), and (iii) the development of the A-type fabric under water-rich conditions (Ohuchi and Irifune, 2013). I will discuss these results based partly on the review of existing results and new results from my lab on olivine morphology. (Miyazaki et al., 2013) reported that substantial LPO develops in diffusion creep in forsterite-diopside aggregates and also the intensity of LPO increases with temperature. They attributed this to the anisotropic crystal morphology of forsterite that appears to depend on temperature. I first note that these results are similar to often observed non-negligible LPO in the diffusion creep (or superplasticity) regime when conditions are close to the boundary to dislocation creep regime (calcite: (Pieri et al., 2001; Walker et al., 1991), perovskite: (Karato et al., 1995)). And in these cases, non-negligible LPO in diffusion creep regime is attributed to the contribution from dislocation glide near the conditions close to the transition to dislocation creep regime. The observed temperature dependence can be interpreted by this model. I will report the results of experimental studies on olivine morphology as a function of temperature to test this model. The causes for the B-type LPO in partially molten olivine, and the A-type LPO under water-rich conditions are enigmatic. Possible causes for these observations will be discussed based partly on the current knowledge of deformation of olivine.

  11. Space weathering simulations through controlled growth of iron nanoparticles on olivine

    NASA Astrophysics Data System (ADS)

    Kohout, T.; Čuda, J.; Filip, J.; Britt, D.; Bradley, T.; Tuček, J.; Skála, R.; Kletetschka, G.; Kašlík, J.; Malina, O.; Šišková, K.; Zbořil, R.

    2014-07-01

    Airless planetary bodies are directly exposed to space weathering. The main spectral effects of space weathering are darkening, reduction in intensity of silicate mineral absorption bands, and an increase in the spectral slope towards longer wavelengths (reddening). Production of nanophase metallic iron (npFe^{0}) during space weathering plays a major role in these spectral changes. A laboratory procedure for the controlled production of npFe^{0} in silicate mineral powders has been developed. The method is based on a two-step thermal treatment of low-iron olivine, first in ambient air and then in a hydrogen atmosphere. Through this process, a series of olivine powder samples was prepared with varying amounts of npFe^{0} in the 7-20-nm size range. A logarithmic trend is observed between the amount of npFe^{0} and darkening, reduction of 1-μ m olivine absorption band, reddening, and the 1-μ m band width. Olivine with a population of physically larger npFe^{0} particles follows spectral trends similar to other samples, except for the reddening trend. This is interpreted as follows: the larger, ˜40-50-nm sized npFe^{0} particles do not contribute to the spectral slope change as efficiently as the smaller npFe^{0} fraction. A linear trend is observed between the amount of npFe^{0} and the 1-μ m band center position, most likely caused by the Fe^{2+} disassociation from the olivine structure into npFe^{0} particles.

  12. Titanium solubility in olivine in the system TiO2 MgO SiO2: no evidence for an ultra-deep origin of Ti-bearing olivine

    NASA Astrophysics Data System (ADS)

    Hermann, J.; O'Neill, H. S. C.; Berry, A. J.

    2005-02-01

    The finding of ilmenite rods in olivine from orogenic peridotites has sparked a discussion about the processes of incorporation and exsolution of titanium in olivine. We have experimentally investigated the solubility of Ti in olivine as a function of composition, temperature and pressure in the synthetic TiO2 MgO SiO2 system. Experiments at atmospheric pressure in the temperature range 1,200 1,500°C showed that the highest concentration of TiO2 is obtained when olivine coexists with spinel (Mg2TiO4). The amount of TiO2 in olivine in the assemblages olivine + spinel + periclase and olivine + spinel + ilmenite at 1,500°C was 1.25 wt.%. Changes in the coexisting phases and decreasing temperature result in a significant reduction of the Ti solubility. Olivine coexisting with pseudobrookite (MgTi2O5) and a Ti Si-rich melt at 1,500°C displays a fourfold lower TiO2 content than when buffered with spinel. A similar decrease in solubility is obtained by a decrease in temperature to 1,200°C. There is a negative correlation between Ti and Si and no correlation between Ti and Mg in Ti-bearing olivine. Together with the established phase relations this suggests that there is a direct substitution of Ti for Si at these temperatures, such that the substituting component has the stoichiometry Mg2TiO4. The unit cell volume of olivine increases systematically with increasing TiO2 content demonstrating that the measured TiO2 contents in olivine are not caused by micro-inclusions but by incorporation of Ti in the olivine structure. Least squares fitting of 20 olivine unit cell volumes against the Ti content yield the relation: V (Å3)=290.12(1) + 23.67(85) NTi. The partial molar volume of end-member Mg2TiO4 olivine (NTi=1) is thus 47.24±0.13 cm3. The change of the Ti solubilty in olivine coexistent with rutile and orthopyroxene with pressure was investigated by piston cylinder experiments at 1,400°C from 15 to 55 kbar. There is no increase in TiO2 contents with pressure and in

  13. Rock magnetic properties of dusty olivine: comparison and calibration of non-heating paleointensity methods

    NASA Astrophysics Data System (ADS)

    Lappe, S. L.; Harrison, R. J.; Feinberg, J. M.

    2012-12-01

    The mechanism of chondrule formation is an important outstanding question in cosmochemistry. Magnetic signals recorded by Fe-Ni nanoparticles in chondrules could carry clues to their origin. Recently, research in this area has focused on 'dusty olivine' in ordinary chondrites as potential carriers of pre-accretionary remanence. Dusty olivine is characterised by the presence of sub-micron Fe-Ni inclusions within the olivine host. These metal particles form via subsolidus reduction of the olivine during chondrule formation and are thought to be protected from subsequent chemical and thermal alteration by the host olivine. Three sets of synthetic dusty olivines have been produced, using natural olivine (average Ni-content of 0.3 wt%), synthetic Ni-containing olivine (0.1wt% Ni) and synthetic Ni-free olivine as starting materials. The starting materials were ground to powders, packed into a 8-27 mm3 graphite crucible, heated up to 1350°C under a pure CO gas flow and kept at this temperature for 10 minutes. After this the samples were held in fixed orientation and quenched into water in a range of known magnetic fields from 0.2 mT to 1.5 mT. We present a comparison of all non-heating methods commonly used for paleointensity determination of extraterrestrial material. All samples showed uni-directional, single-component demagnetization behaviour. Saturation REM ratio (NRM/SIRM) and REMc ratio show non-linear behaviour as function of applied field and a saturation value < 1. Using the REM' method the samples showed approximately constant REM' between 100 and 150 mT AF-field. Plotting the average values for this field range again shows non-linear behaviour and a saturation value < 1. Another approach we examined to obtain calibration curves for paleointensity determination is based on ARM measurents. We also present an analysis of a new FORC-based method of paleointensity determination applied to metallic Fe-bearing samples [1, 2]. The method uses a first-order reversal

  14. Rapid growth of phosphorus-rich olivine in mantle xenolith from Middle Atlas Mountains (Morocco, Africa)

    NASA Astrophysics Data System (ADS)

    Baziotis, Ioannis; Mavrogonatos, Konstantinos; Flemetakis, Stamatios; Papoutsa, Angeliki; Klemme, Stephan; Berndt, Jasper; Asimow, Paul

    2016-04-01

    Phosphorus(P)-rich zones in olivine may reflect incorporation of P in excess of equilibrium partitioning during rapid growth (e.g. Milman-Barris et al. 2008). We investigated a mantle xenolith from Middle Atlas Mountains (Morocco) by optical microscopy and electron microprobe. It contains spinel-bearing lherzolite and orthopyroxenite layers, cross-cut by veins dominated by glass and secondary phases including P-rich olivines. The host lava, presumed to be alkali basalt (El Messbahi et al. 2015), is present on the margins of the hand sample but not included in our thin section. The studied melt veins (MV) generally contain Ol+Gl+Cpx+Pl+Spl±Ap. Olivines in the MV have (Fo72.1‑83.4) with 0.02-0.3 wt.% P2O5; olivines with P2O5 >0.1 wt.% are Fo75.3 ‑82.8. Some olivine grains are inclusion-free; others contain rounded glass inclusions or subhedral spinel or ilmenite inclusions. Olivines is generally found in contact with plagioclase and glass. Glass (5-15 vol%) has variable composition with P2O5 up to 1.52 wt.%, K2O 1.65-2.37 wt%, CaO 6.39-9.55 wt%, Na2O 0.78-6.70 wt% and SiO2 45.2-49.6 wt%. Where glass is in contact with matrix olivine, Fe-rich outer rims on olivine indicate mineral-melt reaction. In MgO variation diagrams, glass compositions display a coherent single trend for all oxides, with the exception of a discrete low-Na group. Clinopyroxene is present both as isolated subhedral to euhedral crystals within the MV and as replacive rims on matrix minerals. Very fine-grained dendritic clinopyroxene quench crystals up to 10 μm long are also present. Plagioclase occurs as prismatic, flow-oriented crystals parallel or sub-parallel to the layering. Spinel shows anhedral and euhedral shapes and occurs both as inclusions in olivine and as discrete grains associated with plagioclase and glass. Spinel in contact with glass shows a spongy outer rim and normal zonation towards Fe-rich rim compositions. Apatite is found mostly as very small crystals embedded in glass

  15. Rapid growth of phosphorus-rich olivine in mantle xenolith from Middle Atlas Mountains (Morocco, Africa)

    NASA Astrophysics Data System (ADS)

    Baziotis, Ioannis; Mavrogonatos, Konstantinos; Flemetakis, Stamatios; Papoutsa, Angeliki; Klemme, Stephan; Berndt, Jasper; Asimow, Paul

    2016-04-01

    Phosphorus(P)-rich zones in olivine may reflect incorporation of P in excess of equilibrium partitioning during rapid growth (e.g. Milman-Barris et al. 2008). We investigated a mantle xenolith from Middle Atlas Mountains (Morocco) by optical microscopy and electron microprobe. It contains spinel-bearing lherzolite and orthopyroxenite layers, cross-cut by veins dominated by glass and secondary phases including P-rich olivines. The host lava, presumed to be alkali basalt (El Messbahi et al. 2015), is present on the margins of the hand sample but not included in our thin section. The studied melt veins (MV) generally contain Ol+Gl+Cpx+Pl+Spl±Ap. Olivines in the MV have (Fo72.1-83.4) with 0.02-0.3 wt.% P2O5; olivines with P2O5 >0.1 wt.% are Fo75.3 -82.8. Some olivine grains are inclusion-free; others contain rounded glass inclusions or subhedral spinel or ilmenite inclusions. Olivines is generally found in contact with plagioclase and glass. Glass (5-15 vol%) has variable composition with P2O5 up to 1.52 wt.%, K2O 1.65-2.37 wt%, CaO 6.39-9.55 wt%, Na2O 0.78-6.70 wt% and SiO2 45.2-49.6 wt%. Where glass is in contact with matrix olivine, Fe-rich outer rims on olivine indicate mineral-melt reaction. In MgO variation diagrams, glass compositions display a coherent single trend for all oxides, with the exception of a discrete low-Na group. Clinopyroxene is present both as isolated subhedral to euhedral crystals within the MV and as replacive rims on matrix minerals. Very fine-grained dendritic clinopyroxene quench crystals up to 10 μm long are also present. Plagioclase occurs as prismatic, flow-oriented crystals parallel or sub-parallel to the layering. Spinel shows anhedral and euhedral shapes and occurs both as inclusions in olivine and as discrete grains associated with plagioclase and glass. Spinel in contact with glass shows a spongy outer rim and normal zonation towards Fe-rich rim compositions. Apatite is found mostly as very small crystals embedded in glass. High

  16. Olivine Weathering in Soil, and Its Effects on Growth and Nutrient Uptake in Ryegrass (Lolium perenne L.): A Pot Experiment

    PubMed Central

    ten Berge, Hein F. M.; van der Meer, Hugo G.; Steenhuizen, Johan W.; Goedhart, Paul W.; Knops, Pol; Verhagen, Jan

    2012-01-01

    Mineral carbonation of basic silicate minerals regulates atmospheric CO2 on geological time scales by locking up carbon. Mining and spreading onto the earth's surface of fast-weathering silicates, such as olivine, has been proposed to speed up this natural CO2 sequestration (‘enhanced weathering’). While agriculture may offer an existing infrastructure, weathering rate and impacts on soil and plant are largely unknown. Our objectives were to assess weathering of olivine in soil, and its effects on plant growth and nutrient uptake. In a pot experiment with perennial ryegrass (Lolium perenne L.), weathering during 32 weeks was inferred from bioavailability of magnesium (Mg) in soil and plant. Olivine doses were equivalent to 1630 (OLIV1), 8150, 40700 and 204000 (OLIV4) kg ha−1. Alternatively, the soluble Mg salt kieserite was applied for reference. Olivine increased plant growth (+15.6%) and plant K concentration (+16.5%) in OLIV4. At all doses, olivine increased bioavailability of Mg and Ni in soil, as well as uptake of Mg, Si and Ni in plants. Olivine suppressed Ca uptake. Weathering estimated from a Mg balance was equivalent to 240 kg ha−1 (14.8% of dose, OLIV1) to 2240 kg ha−1 (1.1%, OLIV4). This corresponds to gross CO2 sequestration of 290 to 2690 kg ha−1 (29 103 to 269 103 kg km−2.) Alternatively, weathering estimated from similarity with kieserite treatments ranged from 13% to 58% for OLIV1. The Olsen model for olivine carbonation predicted 4.0% to 9.0% weathering for our case, independent of olivine dose. Our % values observed at high doses were smaller than this, suggesting negative feedbacks in soil. Yet, weathering appears fast enough to support the ‘enhanced weathering’ concept. In agriculture, olivine doses must remain within limits to avoid imbalances in plant nutrition, notably at low Ca availability; and to avoid Ni accumulation in soil and crop. PMID:22912685

  17. Olivine weathering in soil, and its effects on growth and nutrient uptake in Ryegrass (Lolium perenne L.): a pot experiment.

    PubMed

    ten Berge, Hein F M; van der Meer, Hugo G; Steenhuizen, Johan W; Goedhart, Paul W; Knops, Pol; Verhagen, Jan

    2012-01-01

    Mineral carbonation of basic silicate minerals regulates atmospheric CO(2) on geological time scales by locking up carbon. Mining and spreading onto the earth's surface of fast-weathering silicates, such as olivine, has been proposed to speed up this natural CO(2) sequestration ('enhanced weathering'). While agriculture may offer an existing infrastructure, weathering rate and impacts on soil and plant are largely unknown. Our objectives were to assess weathering of olivine in soil, and its effects on plant growth and nutrient uptake. In a pot experiment with perennial ryegrass (Lolium perenne L.), weathering during 32 weeks was inferred from bioavailability of magnesium (Mg) in soil and plant. Olivine doses were equivalent to 1630 (OLIV1), 8150, 40700 and 204000 (OLIV4) kg ha(-1). Alternatively, the soluble Mg salt kieserite was applied for reference. Olivine increased plant growth (+15.6%) and plant K concentration (+16.5%) in OLIV4. At all doses, olivine increased bioavailability of Mg and Ni in soil, as well as uptake of Mg, Si and Ni in plants. Olivine suppressed Ca uptake. Weathering estimated from a Mg balance was equivalent to 240 kg ha(-1) (14.8% of dose, OLIV1) to 2240 kg ha(-1) (1.1%, OLIV4). This corresponds to gross CO(2) sequestration of 290 to 2690 kg ha(-1) (29 10(3) to 269 10(3) kg km(-2).) Alternatively, weathering estimated from similarity with kieserite treatments ranged from 13% to 58% for OLIV1. The Olsen model for olivine carbonation predicted 4.0% to 9.0% weathering for our case, independent of olivine dose. Our % values observed at high doses were smaller than this, suggesting negative feedbacks in soil. Yet, weathering appears fast enough to support the 'enhanced weathering' concept. In agriculture, olivine doses must remain within limits to avoid imbalances in plant nutrition, notably at low Ca availability; and to avoid Ni accumulation in soil and crop.

  18. Olivine in Martian Meteorite Allan Hills 84001: Evidence for a High-Temperature Origin and Implications for Signs of Life

    NASA Technical Reports Server (NTRS)

    Shearer, C. K.; Leshin, L. A.; Adcock, C. T.

    1999-01-01

    Olivine from Martian meteorite Allan Hills (ALH) 84001 occurs as clusters within orthopyroxene adjacent to fractures containing disrupted carbonate globules and feldspathic shock glass. The inclusions are irregular in shape and range in size from approx. 40 microns to submicrometer. Some of the inclusions are elongate and boudinage-like. The olivine grains are in sharp contact with the enclosing orthopyroxene and often contain small inclusions of chromite The olivine exhibits a very limited range of composition from Fo(sub 65) to Fo(sub 66) (n = 25). The delta(sup 18)O values of the olivine and orthopyroxene analyzed by ion microprobe range from +4.3 to +5.3% and are indistinguishable from each other within analytical uncertainty. The mineral chemistries, O-isotopic data, and textural relationships indicate that the olivine inclusions were produced at a temperature greater than 800 C. It is unlikely that the olivines formed during the same event that gave rise to the carbonates in ALH 84001, which have more elevated and variable delta(sup 18)O values, and were probably formed from fluids that were not in isotopic equilibrium with the orthopyroxene or olivine The reactions most likely instrumental in the formation of olivine could be either the dehydration of hydrous silicates that formed during carbonate precipitation or the reduction of orthopyroxene and spinel If the olivine was formed by either reaction during a postcarbonate beating event, the implications are profound with regards to the interpretations of McKay et al. Due to the low diffusion rates in carbonates, this rapid, high-temperature event would have resulted in the preservation of the fine-scale carbonate zoning' while partially devolatilizing select carbonate compositions on a submicrometer scale. This may have resulted in the formation of the minute magnetite grains that McKay et al attributed to biogenic activity.

  19. Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?

    NASA Astrophysics Data System (ADS)

    Villeneuve, Johan; Chaussidon, Marc; Libourel, Guy

    2011-01-01

    High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ26Mg* enrichments and deficits (calculated in permil as the 26Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ26Mg* (noted δ26Mg*av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from -0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ26Mg*av reflect the formation of the olivines from reservoirs enriched in various amounts of 26Mg by the decay of short-lived 26Al (T1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ26Mg*av value of -0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ26Mg* value of -0.038 ± 0.004‰ (defined at the time of formation of type B Ca-Al-rich inclusions - CAIs - when 26Al/27Al = 5.23 × 10-5, Jacobsen et al., 2008). Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ26Mg*av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ26Mg*av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15- 0. 23+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ26Mg*av values of refractory olivines can be understood if

  20. Composition of primary fluid and melt inclusions in regenerated olivines from hypabyssal kimberlites of the Malokuonapskaya pipe (Yakutia)

    NASA Astrophysics Data System (ADS)

    Tomilenko, A. A.; Kuzmin, D. V.; Bulbak, T. A.; Timina, T. Yu.; Sobolev, N. V.

    2015-11-01

    The primary fluid and melt inclusions in regenerated zonal crystals of olivine from kimberlites of the Malokuonapskaya pipe were first examined by means of microthermometry, optic and scanning electron microscopy, and Raman spectroscopy. The high-pressure genesis of homogenous central parts of the olivines was revealed, probably under intense metasomatism at early hypogene stages with subsequent regeneration in the kimberlitic melt. The olivine crystals were regenerated from silicate-carbonate melts at about 1100°C. The composition of the kimberlitic melt was changed by way of an increase in the calcium content.

  1. Mineralogy and Petrology of Amoeboid Olivine Inclusions in CO3 Chondrites: Relationship to Parent-Body Aqueous Alteration

    NASA Technical Reports Server (NTRS)

    Chizmadia, Lysa J.; Rubin, Alan E.; Wasson, John T.

    2003-01-01

    Petrographic and mineralogic studies of amoeboid olivine inclusions (AOIs) in CO3 carbonaceous chondrites reveal that they are sensitive indicators of parent-body aqueous and thermal alteration. As the petrologic subtype increases from 3.0 to 3.8, forsteritic olivine (Fa(sub 0-1)) is systematically converted into ferroan olivine (Fa(sub 60-75)). We infer that the Fe, Si and O entered the assemblage along grain boundaries, forming ferroan olivine that filled fractures and voids. As temperatures increased, Fe(+2) from the new olivine exchanged with Mg(+2) from the original AOI to form diffusive haloes around low-FeO cores. Cations of Mn(+2), Ca(+2) and Cr(+3) were also mobilized. The systematic changes in AOI textures and olivine compositional distributions can be used to refine the classification of CO3 chondrites into subtypes. In subtype 3.0, olivine occurs as small forsterite grains (Fa(sub 0-1)), free of ferroan olivine. In petrologic subtype 3.2, narrow veins of FeO-rich olivine have formed at forsterite grain boundaries. With increasing alteration, these veins thicken to form zones of ferroan olivine at the outside AOI margin and within the AOI interior. By subtype 3.7, there is a fairly broad olivine compositional distribution in the range Fa(sub 63-70), and by subtype 3.8, no forsterite remains and the high-Fa peak has narrowed, Fa(sub 64-67). Even at this stage, there is incomplete equilibration in the chondrite as a whole (e.g., data for coarse olivine grains in Isna (CO3.8) chondrules and lithic clasts show a peak at Fa(sub39)). We infer that the mineral changes in A01 identified in the low petrologic types required aqueous or hydrothermal fluids whereas those in subtypes greater than or equal to 3.3 largely reflect diffusive exchange within and between mineral grains without the aid of fluids.

  2. XANES Measurements of Cr Valence in Olivine and their Applications to Planetary Basalts (Invited)

    NASA Astrophysics Data System (ADS)

    Bell, A. S.; Burger, P.; Le, L.; Shearer, C. K.; Papike, J.; Sutton, S. R.; Newville, M.; Jones, J. H.

    2013-12-01

    The oxidation state and partitioning behavior of trace Cr in terrestrial and planetary basaltic magmas has long been a subject of petrologic inquiry. We have performed a series of experiments designed to examine the relationship between oxygen fugacity and the ratio of divalent to trivalent Cr present in olivine crystals grown from a basaltic liquid. The experimental olivine crystals were grown at fO2 values ranging from IW-1 to IW+3.4. The melt composition used in this work was modeled after the bulk composition of the primitive, basaltic martian meteorite Yamato 980459 (Y-98). Chromium valence in the olivine crystals was measured with X-ray-Absorption-Near-Edge-Spectroscopy (XANES) at the Advanced Photon Source, Argonne National Laboratory. Chromium K-edge XANES data were acquired with the x-ray microprobe of GSECARS beamline 13-ID-E. Beam focusing was accomplished with dynamically-figured Kirkpatrick-Baez focusing mirrors; this configuration yielded a beam focused to a final spot size of ~ 4 μm2. Results from the XANES measurements indicate that the ratio of divalent to trivalent Cr in the olivine is systematically correlated with fO2 in a manner that is consistent with the expected redox systematics for Cr2+- Cr3+ in the melt. In this way, measurements of the Cr2+/Cr3+ in olivine phenocrysts can indirectly reveal information about the Cr valence ratio and fO2 the liquid from which it grew even in the absence of a quenched melt phase. Although the results from the experiments presented in this work specifically apply to the Yamato 98 parental liquid, the concepts and XANES analytical techniques used in this study present a novel, generalized methodology that may be applicable to any olivine-bearing basalt. Furthermore, the XANES based measurements are made on a micron-scale, thus potential changes of the Cr2+/Cr3+ in the melt occurring during crystallization may be recorded in detail.

  3. Unusual spin fluctuations and magnetic frustration in olivine and non-olivine LiCoPO4 detected by P31 and Li7 nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Baek, S.-H.; Klingeler, R.; Neef, C.; Koo, C.; Büchner, B.; Grafe, H.-J.

    2014-04-01

    We report P31 and Li7 nuclear magnetic resonance (NMR) studies in new non-olivine LiZnPO4-type LiCoPO4tetra microcrystals, where the Co2+ ions are tetrahedrally coordinated. Olivine LiCoPO4, which was directly transformed from LiCoPO4tetra by an annealing process, was also studied and compared. The uniform bulk magnetic susceptibility and the P31 Knight shift obey the Curie-Weiss law for both materials with a high spin Co2+ (3d7, S =3/2), but the Weiss temperature Θ and the effective magnetic moment μeff are considerably smaller in LiCoPO4tetra. The spin-lattice relaxation rate T1-1 reveals a quite different nature of the spin dynamics in the paramagnetic state of both materials. Our NMR results imply that strong geometrical spin frustration occurs in tetrahedrally coordinated LiCoPO4, which may lead to the incommensurate magnetic ordering.

  4. Magnetic petrology of eastern North America diabases. I - Olivine-normative dikes from western South Carolina

    NASA Technical Reports Server (NTRS)

    Warner, Richard D.; Wasilewski, Peter J.

    1990-01-01

    The oxide mineralogy and the magnetic behavior of 15 olivine-normative samples obtained from South-Caroline diabase dikes were investigated using electron microprobe and SEM analyses and measurements of natural remanence magnetization (NRM), saturation isothermal remanence magnetization (SIRM), and anhysteritic remanence magnetization. It was found that chromite (which for these olivine-normative diabases is a sensitive petrologic indicator) constitutes up to 0.5 vol pct and that its abundance and composition correlate with bulk rock Cr. Microscopic analyses showed that titanomagnetite compositions were mostly between 0.4 and 0.55. The values of NRM and the NRM/SIRM ratios varied between 4 and 0.01 A sq m/kg and 0.0019 and 0.032, respectively. These properties inversely correlate with Cr content and demonstrably contrast Cr-rich and Cr-poor samples.

  5. Elasticity of iron-bearing olivine polymorphs investigated by first principles

    NASA Astrophysics Data System (ADS)

    Núñez Valdez, Maribel; Yu, Yonggang; Wentzcovitch, Renata

    2011-03-01

    We calculate by first principles the effect of iron on the high pressure-temperature elasticity of olivine polymorphs: α -phase (olivine), β -phase (wadsleyite) and γ -phase (ringwoodite), the major constituents of the Earth's upper mantle and transition zone (TZ). We combine the LDA, the quasiharmonic approximation, and a model vibrational density of states for the solid solution to calculate the full elastic tensor Cij , bulk (K) and shear (G) moduli of (Mg 0.875 Fe 0.125)2 Si O4 . Comparison with experimental data at ambient conditions validates our results. In the pressure and temperature range of the upper mantle and TZ we study single crystal wave propagation anisotropy and polarization anisotropy in aggregates with preferred orientation. Research supported by NSF EAR-1019853 and EAR-0810272. Computations were performed at the Minnesota Supercomputing Institute.

  6. Alteration of Al-rich inclusions inside amoeboid olivine aggregates in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Hashimoto, Akihiko; Grossman, Lawrence

    1987-01-01

    The primary phases of Al-rich inclusions in amoeboid olivine aggregates have undergone alteration reactions with the solar nebular gas. The simplest interpretation of the present observations is that melilite was the first primary phase to disappear with falling temperature, and was replaced by grossular + anorthite + feldspathoids, followed by fassaite; spinel was the last phase to be altered. Thermodynamic calculations suggest that Na-rich phlogopite could have formed at about 470 K and chlorite at about 328 K at a water fugacity of 0.000001, which is that of a gas of solar composition in this temperature range. The olivine around Al-rich inclusions is not serpentized, indicating the cessation of gas-solid equilibrium above 274 K.

  7. THE IRRADIATION-INDUCED OLIVINE TO AMORPHOUS PYROXENE TRANSFORMATION PRESERVED IN AN INTERPLANETARY DUST PARTICLE

    SciTech Connect

    Rietmeijer, Frans J. M.

    2009-11-01

    Amorphization of crystalline olivine to glass with a pyroxene composition is well known from high-energy irradiation experiments. This report is on the first natural occurrence of this process preserved in a chondritic aggregate interplanetary dust particle. The Fe-rich olivine grain textures and compositions and the glass grain compositions delineate this transformation that yielded glass with Fe-rich pyroxene compositions. The average glass composition, (Mg, Fe){sub 3}Si{sub 2}O{sub 7}, is a serpentine-dehydroxylate with O/Si = 3.56 +- 0.25, (Mg+Fe)/Si = 1.53 +- 0.24, and Mg/(Mg+Fe) = 0.74 +- 0.1. These measured atomic ratios match the ratios that have been proposed for amorphous interstellar silicate grains very well, albeit the measured Mg/(Mg+Fe) ratio is lower than was proposed for amorphous interstellar silicate grains, Mg/(Mg+Fe) > 0.9.

  8. Origins and Distribution of Chondritic Olivine Inferred from Wild 2 and Chondrite Matrix

    NASA Technical Reports Server (NTRS)

    Frank, D. R.; Zolensky, M. E.

    2014-01-01

    To date, only 180 particle impact tracks from Wild 2 have been extracted from the Stardust aerogel collector and even fewer have been thoroughly characterized. In order to provide a cohesive compositional dataset that can be compared to the meteorite record, we have made both major and minor element analyses (TEM/EDXS) of olivine and low-Ca pyroxene for 39 particles harvested from 26 tracks. However, the dearth of equivalent analyses for these phases in chondrite matrix hinders their comparison to the Wild 2 samples. To properly permit comparison of chondritic olivine and pyroxene to the Wild 2 samples, we have also provided a large, comprehensive EPMA dataset (greater than10(exp 3) analyses) of analogous grains (5-30 micrometers) isolated in L/LL3.0-4, CI, CM, CR, CH, CO, CV, Acfer 094, EH3, EL6, and Kakangari matrix

  9. Geology and petrology of the Voisey's Bay intrusion: reaction of olivine with sulfide and silicate liquids

    NASA Astrophysics Data System (ADS)

    Li, C.; Naldrett, A. J.

    1999-06-01

    The Voisey's Bay Ni-Cu-Co sulfide deposit is located in Eastern Labrador, and transects the 1.85 Ga collisional boundary between interbanded garnet-sillimanite and quartzo-feldspathic paragneisses (Tasuiyak gneisses) of the Proterozoic Churchill Province to the west and granitic, intermediate and mafic orthogneisses of the Archean Nain Province to the east. The deposit is associated with an upper troctolitic chamber (the Eastern Deeps chamber) which is connected to a lower troctolitic chamber (the Reid Brook chamber) by a gabbroic/troctolitic feeder sheet approximately 1 km in vertical extent. Rock sequences that have been defined to date include Leuco-troctolite (LUT) in the Reid Brook chamber, Feeder Breccia (FB) in the Reid Brook Zone, Feeder Olivine Gabbro (FOG), Leopard Troctolite (LT) and Basal Breccia Sequence (BBS) in the feeder sheet, and Olivine Gabbro (OG), Normal Troctolite (NT) and Varied-textured Troctolite (VT) in the Eastern Deeps chamber. Mineralisation has been found in the feeder sheet, as massive stringers in gneisses flanking the feeder, in the `Ovoid', a 600×300×110 m 3 basin of massive sulfide at surface, and as a zone of massive sulfide that has developed close to the entry of the feeder to the Eastern Deeps chamber. The mineralisation comprises pyrrhotite (both hexagonal and troilite in varying proportions), pentlandite, chalcopyrite, magnetite and minor cubanite. An important component of all mineralized zones is a breccia of gneissic fragments in a troctolitic to noritic matrix referred to as BBS or FB. Considerable reaction has occurred between the troctolite magma and the gneiss inclusions. Olivines in the LUT, OG and FOG have low Ni contents relative to their forsterite (Fo) contents. Olivines in the NT and VT have higher Ni contents but show a great scatter in both their Ni and Fo contents. The Ni content of olivine in the LT increases systematically with decreasing Fo content. All of these variations are explained in terms of

  10. Ar-Ar and Rb-Sr Ages of the Tissint Olivine-phyric Martian Shergottite

    NASA Technical Reports Server (NTRS)

    Park, J.; Herzog, G. F.; Nyquist, L. E.; Shih, C.-Y.; Turin, B.; Lindsay, F. N.; Delaney, J. S.; Swisher, C. C., III; Agee, C.

    2013-01-01

    The fifth martian meteorite fall, Tissint, is an olivine-phyric shergottite that contains olivine macrocrysts (approximately 1.5 mm) [1]. [2] reported the Sm-Nd age of Tissint as 596 plus or minus 23 Ma along with Rb-Sr data that defined no isochron. [3] reported Lu-Hf and Sm-Nd ages of 583 plus or minus 86 Ma and 616 plus or minus 67 Ma, respectively. The cosmic-ray exposure ages of Tissint are 1.10 plus or minus 0.15 Ma based on 10Be [4], and 1.0-1.1 Ma, based on 3He, 21Ne, and 38Ar [5,6].We report Ar-Ar ages and Rb-Sr data.

  11. Petrology of Amoeboid Olivine Aggregates in Antarctic CR Chondrites: Comparison With Other Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Komatsu, M.; Fagan, T. J.; Yamaguchi, A.; Mikouchi, T.; Zolensky, M. E.; Yasutake, M.

    2016-01-01

    Amoeboid olivine aggregates (AOAs) are important refractory components of carbonaceous chondrites and have been interpreted to represent solar nebular condensates that experienced high-temperature annealing, but largely escaped melting. In addition, because AOAs in primitive chondrites are composed of fine-grained minerals (forsterite, anorthite, spinel) that are easily modified during post crystallization alteration, the mineralogy of AOAs can be used as a sensitive indicator of metamorphic or alteration processes. AOAs in CR chondrites are particularly important because they show little evidence for secondary alteration. In addition, some CR AOAs contain Mn-enriched forsterite (aka low-iron, Mn-enriched or LIME olivine), which is an indicator of nebular formation conditions. Here we report preliminary results of the mineralogy and petrology of AOAs in Antarctic CR chondrites, and compare them to those in other carbonaceous chondrites.

  12. Diffusion-driven magnesium and iron isotope fractionation in Hawaiian olivine

    USGS Publications Warehouse

    Teng, F.-Z.; Dauphas, N.; Helz, R.T.; Gao, S.; Huang, S.

    2011-01-01

    Diffusion plays an important role in Earth sciences to estimate the timescales of geological processes such as erosion, sediment burial, and magma cooling. In igneous systems, these diffusive processes are recorded in the form of crystal zoning. However, meaningful interpretation of these signatures is often hampered by the fact that they cannot be unambiguously ascribed to a single process (e.g., magmatic fractionation, diffusion limited transport in the crystal or in the liquid). Here we show that Mg and Fe isotope fractionations in olivine crystals can be used to trace diffusive processes in magmatic systems. Over sixty olivine fragments from Hawaiian basalts show isotopically fractionated Mg and Fe relative to basalts worldwide, with up to 0.4??? variation in 26Mg/24Mg ratios and 1.6??? variation in 56Fe/54Fe ratios. The linearly and negatively correlated Mg and Fe isotopic compositions [i.e., ??56Fe=(??3.3??0.3)????26Mg], co-variations of Mg and Fe isotopic compositions with Fe/Mg ratios of olivine fragments, and modeling results based on Mg and Fe elemental profiles demonstrate the coupled Mg and Fe isotope fractionation to be a manifestation of Mg-Fe inter-diffusion in zoned olivines during magmatic differentiation. This characteristic can be used to constrain the nature of mineral zoning in igneous and metamorphic rocks, and hence determine the residence times of crystals in magmas, the composition of primary melts, and the duration of metamorphic events. With improvements in methodology, in situ isotope mapping will become an essential tool of petrology to identify diffusion in crystals. ?? 2011 Elsevier B.V.

  13. Geometrically necessary dislocation densities in olivine obtained using high-angular resolution electron backscatter diffraction.

    PubMed

    Wallis, David; Hansen, Lars N; Ben Britton, T; Wilkinson, Angus J

    2016-09-01

    Dislocations in geological minerals are fundamental to the creep processes that control large-scale geodynamic phenomena. However, techniques to quantify their densities, distributions, and types over critical subgrain to polycrystal length scales are limited. The recent advent of high-angular resolution electron backscatter diffraction (HR-EBSD), based on diffraction pattern cross-correlation, offers a powerful new approach that has been utilised to analyse dislocation densities in the materials sciences. In particular, HR-EBSD yields significantly better angular resolution (<0.01°) than conventional EBSD (~0.5°), allowing very low dislocation densities to be analysed. We develop the application of HR-EBSD to olivine, the dominant mineral in Earth's upper mantle by testing (1) different inversion methods for estimating geometrically necessary dislocation (GND) densities, (2) the sensitivity of the method under a range of data acquisition settings, and (3) the ability of the technique to resolve a variety of olivine dislocation structures. The relatively low crystal symmetry (orthorhombic) and few slip systems in olivine result in well constrained GND density estimates. The GND density noise floor is inversely proportional to map step size, such that datasets can be optimised for analysing either short wavelength, high density structures (e.g. subgrain boundaries) or long wavelength, low amplitude orientation gradients. Comparison to conventional images of decorated dislocations demonstrates that HR-EBSD can characterise the dislocation distribution and reveal additional structure not captured by the decoration technique. HR-EBSD therefore provides a highly effective method for analysing dislocations in olivine and determining their role in accommodating macroscopic deformation. PMID:27337604

  14. Viscous anisotropy of textured olivine aggregates, Part 1: Measurement of the magnitude and evolution of anisotropy

    NASA Astrophysics Data System (ADS)

    Hansen, Lars N.; Warren, Jessica M.; Zimmerman, Mark E.; Kohlstedt, David L.

    2016-07-01

    The development of crystallographic textures in olivine-rich rocks leads to a marked anisotropy in viscosity of the upper mantle, strongly influencing a variety of large-scale geodynamic processes. Most estimates of the magnitude of viscous anisotropy in the upper mantle are derived from micromechanical models that predict textural and mechanical evolution numerically. Unfortunately, relatively few data exist with which to benchmark these models, and therefore their applicability to geodynamic processes remains in question. Here we present the results from a series of laboratory deformation experiments that yield insight into the magnitude and evolution of the anisotropy of olivine aggregates during deformation along complex loading paths. Aggregates of Fo50 olivine were first deformed in extension in a gas-medium apparatus at a temperature of 1473 K, confining pressure of 300 MPa, and a variety of stresses and strain rates. Early in the extension experiments, samples exhibited viscosities similar to those previously determined for isotropic aggregates. Extensional deformation was accompanied by formation of crystallographic textures with [100] axes dominantly aligned with the extension axis. Samples were subsequently deformed in torsion under similar conditions to shear strains of up to 15.5. Early in the torsion experiments, samples supported stresses a factor of ∼2 larger than measured at the end of extension experiments, demonstrating a marked anisotropy in viscosity. Textures at the end of torsion experiments exhibited [100] axes dominantly aligned with the shear direction, comparable to previous experimental observations. Evolution of the textures resulting from extension to those resulting from torsion was analyzed through examination of radial sections of torsion samples. Our results confirm that texture produces viscous anisotropy in olivine aggregates, and we provide a simple, calibrated parameterization of viscous anisotropy for use in geodynamic

  15. Chondrule Pyroxene Embedded in Cores of Amoeboid Olivine Aggregates from Allende: Evidence of Overlapping Formation Times of AOAs and Chondrules

    NASA Astrophysics Data System (ADS)

    Fagan, T. J.; Komatsu, M.; Nishijima, E.; Fukushima, H.; Yasuda, T.

    2016-08-01

    Coarse low-Ca pyroxene has been identified in two amoeboid olivine aggregates in the CV3 Allende. The pyroxene crystals appear to be relict chondrule phenocrysts. If so, the texture indicates overlapping formation times of AOAs and chondrules.

  16. Temperature Dependence of Individual Absorptions Bands in Olivine: Implications for Inferring Compositions of Asteroid Surfaces from Spectra

    NASA Technical Reports Server (NTRS)

    Sunshine, J. M.; Hinrichs, J. L.; Lucey, P. G.

    2000-01-01

    The temperature variations of individual absorptions in olivine are modeled and found to narrow, move slightly in position, and change in relative strength as predicted by theory. These thermal changes may be confused with compositional differences.

  17. Water in Olivine, Clinopyroxenen and Plagioclase of Lunar Meteorites of the NWA 773 Clan by IR Micro-Spectrosocpy

    NASA Astrophysics Data System (ADS)

    Kayama, M.; Nakashima, S.; Tomioka, N.; Ohtani, E.; Seto, Y.; Nagaoka, H.; Ozawa, S.; Sekine, T.; Miyahara, M.; Miyake, A.; Götze, J.; Tomeoka, K.

    2016-08-01

    Water in olivine, clinopyroxene and plagioclase of gabbroic lunar meteorites of Northwest Africa 2977 and 6950 and gabbroic/basaltic brecciated lunar meteorite of NWA 2727 were characterized by in-situ Fourier-transform infrared micro-spectroscopy.

  18. Olivine flotation and settling experiments on the join Mg2SiO4-Fe2SiO4

    NASA Technical Reports Server (NTRS)

    Herzberg, C. T.; Baker, M. B.; Wendlandt, R. F.

    1982-01-01

    Results are presented of a study of some unusual density relations between olivine and coexisting liquid in the system fosterite-fayalite. At 1 atmosphere pressure it is found that olivine floats on its coexisting liquid for intermediate compositions on this binary because of extreme partitioning of Fe into the melt phase. At 20 kilobars, the usual behavior of olivine settling is found to occur because the partitioning of Fe in the melt is reduced, aided possibly by the dissolution of CO2 in the melt from the use of a graphite container. It is determined that olivine flotation and settling are rapid in a time period of only a few hours because viscosities are slightly greater than that of paraffin oil at room temperature. Some adcumulate textures with good triple junction grain boundaries are found to be developed. Observations of differentiated magmatic systems suggest that the mechanisms by which magmas can differentiate vary considerably in the ultramafic to tholeiitic compositional range.

  19. An experimental study of trace element partitioning between olivine, orthopyroxene and melt in chondrules - Equilibrium values and kinetic effects

    NASA Technical Reports Server (NTRS)

    Kennedy, A. K.; Lofgren, G. E.; Wasserburg, G. J.

    1993-01-01

    Mineral/melt partition coefficients were measured using an ion microprobe for 32 elements in orthopyroxene and olivine in equilibrium and dynamic crystallization experiments on compositions corresponding to chondrules. The mineral/melt partition coefficients calculated from the measured concentrations for both olivine and orthopyroxene show very little change between equilibrium experiments and dynamic experiments with cooling rates of up to 100 C/h. The results provide a self-consistent set of partition coefficients that can be used in thermodynamic models of equilibrium and kinetic partitioning between olivine, orthopyroxene, and melt. These data can be used in models of partial melting and crystal fractionation in olivine- and orthopyroxene-rich systems, such as chondrules. The results may also be applicable to mantle peridotites, komatiitic and picritic lavas, and ultramafic intrusions.

  20. Morphological changes of olivine grains reacted with amino acid solutions by impact process

    NASA Astrophysics Data System (ADS)

    Umeda, Yuhei; Takase, Atsushi; Fukunaga, Nao; Sekine, Toshimori; Kobayashi, Takamichi; Furukawa, Yoshihiro; Kakegawa, Takeshi

    2016-10-01

    Early oceans on Earth might have contained certain amounts of biomolecules such as amino acids, and they were subjected to meteorite impacts, especially during the late heavy bombardment. We performed shock recovery experiments by using a propellant gun in order to simulate shock reactions among olivine as a representative meteorite component, water and biomolecules in oceans in the process of marine meteorite impacts. In the present study, recovered solid samples were analyzed by using X-ray powder diffraction method, scanning electron microscopy, electron probe microanalysis, and transmission electron microscopy with energy-dispersive X-ray spectrometry. The analytical results on shocked products in the recovered sample showed (1) morphological changes of olivine to fiber- and bamboo shoot-like crystals, and to pulverized grains; and features of lumpy surfaces affected by hot water, (2) the formation of carbon-rich substances derived from amino acids, and (3) the incorporation of metals from container into samples. According to the present results, fine-grained olivine in meteorites might have morphologically changed and shock-induced chemical reactions might have been enhanced so that amino acids related to the origin of life may have transformed to carbon-rich substances by impacts.

  1. Extracting Olivine (Fo-Fa) Compositions from Raman Spectral Peak Positions

    NASA Technical Reports Server (NTRS)

    Kuebler, K.; Jolliff, B. J.; Wang, Alian; Haskin, L. A.

    2005-01-01

    Olivine and pyroxene are two major basaltic minerals that have been identified at Gusev Crater and Meridiani Planum by the Mars Exploration Rovers. Full petrologic characterization of a sample (rock or soil), however, requires determining the range of mineral compositions, extent of zoning, range of grain sizes, mineral associations, presence of xenocrysts, etc. Information of this sort will aid the interpretation of sample crystallization and differentiation histories and help discriminate between lithologies. In Raman spectroscopic experiments, minerals are identified by their spectral patterns and mineral compositions can be inferred from the peak positions. Instruments currently in use or slated for impending surface exploration missions provide only average elemental compositions for relatively large rock or soil targets or bulk mineral analysis. No techniques currently in use or scheduled for flight can characterize both structure and composition of individual mineral grains, in-situ, like the Mars Microbeam Raman Spectrometer (MMRS). The MMRS is designed to take 100 spectra along a 1 cm linear traverse on the surface of a sample, with contributions from one or a few mineral phases per spectrum. We presented a method to extract structural and compositional information from the Raman spectra of quadrilateral pyroxenes. The pyroxene calibration was applied to a Raman spectroscopic study of Martian meteorite EETA79001 along with a preliminary olivine calibration, where we demonstrated the capability to discriminate related lithologies using Raman point counts. This paper presents an improved olivine calibration that will further aid sample characterization and the study of alteration processes.

  2. Igneous cooling history of olivine-phyric shergottite Yamato 980459 constrained by dynamic crystallization experiments

    NASA Astrophysics Data System (ADS)

    First, Emily; Hammer, Julia

    2016-07-01

    Dynamic crystallization experiments were performed on a liquid having the bulk composition of olivine-phyric shergottite Yamato 980459, to constrain the igneous thermal history of this meteorite. Key characteristics of the meteorite's mineralogy and texture, including several morphologically distinct olivine and pyroxene crystal populations and a glassy mesostasis devoid of plagioclase, were replicated upon cooling from 1435 to 909 °C at 1 atmosphere under reducing conditions. Three sequential cooling ramps are required to produce synthetic samples with textures and compositions matching Yamato 980459. Olivine phenocrysts formed at <1 °C h-1, presumably at depth in the Martian crust. Pyroxene phenocrysts formed mainly at ~10 °C h-1, consistent with crystallization within a lava flow at depths of 25-45 cm. Increased cooling rate (~100 °C h-1) in a third stage suppressed the formation of plagioclase and produced groundmass crystals, consistent with crystallization at lava flow depths of 5-7 cm. Although Y 980459 is unique among Martian meteorites (i.e., preserving a primary glassy mesostasis), its emplacement did not require unique physical conditions. Rather, the second and third cooling stages may reflect cooling within the core of a pāhoehoe-like flow and subsequent breakout on the surface of Mars.

  3. Trace elements of olivine in silicate inclusions of IAB iron meteorites reflecting low-temperature history

    NASA Astrophysics Data System (ADS)

    Zipfel, J.; Weinbruch, S.; Specht, S.; Palme, H.

    1994-07-01

    IAB iron meteorites with silicate inclusions may have formed at the core-mantle boundary of planetary bodies. Important constraints on the thermal evolution and the size of these bodies are given by cooling rates obtained from these meteorites. Recent metallographic cooling rates determined in metal grains enclosed in silicates of IAB irons are between 30 and 70 C/m.y. An independent method for obtaining cooling rates of IAB silicates inclusions was suggested by Kohler (1991). The Ca contents of olivines are zoned from core to rim reflecting cooling from about 650 to 500 C, at similar temperatures as kamacite-taenite exsolution occurs. Calcium zoning of ol was observed in Landes, Caddo County, Woodbine, and Persimmon Creek (recent ion microprobe data). In addition, the central Ca content of olivine grains of different IAB meteorites should also reflect cooling rates. Olivine core compositions in silicates of several IAB meteorites, e.g., Persimmon Creek (PC), El Taco (ET), Woodbine (WB), Landes (LA), Caddo County (CC), and Copiapo (COP) were determined with the electron microprobe. Results of the electron microporbe study are discussed. The use of Ca core contents and Ca profiles as indicators of low-temperature cooling rates requires further work. Nickel in ol may provide additional constraints on the thermal histories.

  4. Modal abundances of pyroxene, olivine, and mesostasis in nakhlites: Heterogeneity, variation, and implications for nakhlite emplacement

    NASA Astrophysics Data System (ADS)

    Corrigan, Catherine M.; Velbel, Michael A.; Vicenzi, Edward P.

    2015-09-01

    Nakhlites, clinopyroxenite meteorites from Mars, share common crystallization and ejection ages, suggesting that they might have been ejected from the same place on Mars by the same ejection event (impact) and are different samples of the same thick volcanic flow unit or shallow sill. Mean modal abundances and abundance ranges of pyroxene, olivine, and mesostasis vary widely among different thin-sections of an individual nakhlite. Lithologic heterogeneity is the main factor contributing to the observed modal-abundance variations measured in thin-sections prepared from different fragments of the same stone. Two groups of nakhlites are distinguished from one another by which major constituent varies the least and the abundance of that constituent. The group consisting of Nakhla, Lafayette, Governador Valadares, and the Yamato nakhlite pairing group is characterized by low modal mesostasis and pyroxene-olivine covariance, whereas the group consisting of the Miller Range nakhlite pairing group and Northwest Africa 5790 is characterized by low modal olivine and pyroxene-mesostasis covariance. These two groups sample the slowest-cooled interior portion and the chilled margin, respectively, of the nakhlite emplacement body as presently understood, and appear to be also related to recently proposed nakhlite groups independently established using compositional rather than petrographic observations. Phenocryst modal abundances vary with inferred depth in the nakhlite igneous body in a manner consistent with solidification of the nakhlite stack from dynamically sorted phenocryst-rich magmatic crystal-liquid mush.

  5. Two-Stage Deformation of Olivine Aggregates with Changing Deformation Kinematics

    NASA Astrophysics Data System (ADS)

    Mahan, B. M.; Skemer, P. A.; Griera, A.

    2011-12-01

    Two-stage deformation experiments have been conducted on synthetic olivine aggregates to investigate the influence of pre-existing fabric on the evolution of lattice-preferred orientation (LPO), seismic anisotropy, and grain morphology. This study is motivated by recent work on naturally and experimentally deformed peridotites, which suggest that the alignment of olivine axes with the shear plane requires more strain in samples with a strong pre-existing LPO than in samples with weak or random LPO. In the first stage of deformation, aggregates synthesized from San Carlos olivine are deformed at P = 1 GPa and T = 1500 K in a triaxial geometry to produce axi-symmetric LPOs of varying strength. In a second stage of deformation, the aggregates are re-deformed in simple shear to varying shear strains. Microstructural analyses are performed after each step (synthesis, triaxial deformation, simple shear deformation) using optical microscopy and electron backscatter diffraction (EBSD). These results are compared to numerical models of microstructural evolution. Our results provide constraints on the evolution of LPO and consequent seismic signature as a function of preexisting rock fabric. These data are necessary to interpret seismic anisotropy in settings where kinematics are complex, such as mid-ocean ridges and subduction zones.

  6. Processes and time scales of magmatic evolution as revealed by Fe-Mg chemical and isotopic zoning in natural olivines

    NASA Astrophysics Data System (ADS)

    Oeser, Martin; Dohmen, Ralf; Horn, Ingo; Schuth, Stephan; Weyer, Stefan

    2015-04-01

    In this study, we applied high-precision in situ Fe and Mg isotope analyses by femtosecond laser ablation (fs-LA) MC-ICP-MS on chemically zoned olivine xeno- and phenocrysts from intra-plate volcanic regions in order to investigate the magnitude of Fe and Mg isotope fractionation and its suitability to gain information on magma evolution. Our results show that chemical zoning (i.e., Mg#) in magmatic olivines is commonly associated with significant zoning in δ56Fe and δ26Mg (up to 1.7‰ and 0.7‰, respectively). We explored different cases of kinetic fractionation of Fe and Mg isotopes by modeling diffusion in the melt or olivine and simultaneous growth or dissolution. Combining the information of chemical and isotopic zoning in olivine allows to distinguish between various processes that may occur during magma evolution, namely diffusive Fe-Mg exchange between olivine and melt, rapid crystal growth, and Fe-Mg inter-diffusion simultaneous to crystal dissolution or growth. Chemical diffusion in olivine appears to be the dominant process that drives isotope fractionation in magmatic olivine. Simplified modeling of Fe and Mg diffusion is suitable to reproduce both the chemical and the isotopic zoning in most of the investigated olivines and, additionally, provides time information about magmatic processes. For the Massif Central (France), modeling of diffusive re-equilibration of mantle olivines in basanites revealed a short time span (<2 years) between the entrainment of a mantle xenolith in an intra-plate basaltic magma and the eruption of the magma. Furthermore, we determined high cooling rates (on the order of a few tens to hundreds of °C per year) for basanite samples from a single large outcrop in the Massif Central, which probably reflects the cooling of a massive lava flow after eruption. Results from the modeling of Fe and Mg isotope fractionation in olivine point to a systematic difference between βFe and βMg (i.e., βFe/βMg ≈ 2), implying that the

  7. Partition coefficients for Al, Ca, Ti, Cr, and Ni in olivine obtained by melting experiment on an LL6 chondrite

    NASA Technical Reports Server (NTRS)

    Miyamoto, M.; Mikouchi, T.; Mckay, G. A.

    1994-01-01

    We report the partition coefficients for Ca, Al, Ti, Cr, and Ni in olivine obtained through a series of melting experiments on an LL6 chondrite under varying conditions of temperature and oxygen fugacity. It is necessary to examine the variation of partition coefficients up to extremely reducing conditions in order to study meteoritic olivines. For Ca, Al, and Cr, the partition coefficients tend to decrease as temperature increases, but do not change even under extremely reducing conditions.

  8. Characterization of olivine fabrics and mylonite in the presence of fluid and implications for seismic anisotropy and shear localization

    NASA Astrophysics Data System (ADS)

    Jung, Sejin; Jung, Haemyeong; Austrheim, Håkon

    2015-04-01

    The Lindås Nappe, Bergen Arc, is located in western Norway and displays two high-grade metamorphic structures. A Precambrian granulite facies foliation is transected by Caledonian fluid-induced eclogite-facies shear zones and pseudotachylytes. To understand how a superimposed tectonic event may influence olivine fabric and change seismic anisotropy, two lenses of spinel lherzolite were studied by SEM and EBSD techniques. The granulite foliation of the surrounding anorthosite complex is displayed in ultramafic lenses as a modal variation in olivine, pyroxenes and spinel, and the Caledonian eclogite-facies structure in the surrounding anorthosite gabbro is represented by thin (<1 cm) garnet-bearing ultramylonite zones. The olivine fabrics in the spinel bearing assemblage were E-type and B-type and a combination of A- and B-type LPOs. There was a change in olivine fabric from a combination of A- and B-type LPOs in the spinel bearing assemblage to B- and E-type LPOs in the garnet lherzolite mylonite zones. FTIR analyses reveal that the water content of olivine in mylonite is much higher (~600 ppm H/Si) than that in spinel lherzolite (~350 ppm H/Si), indicating that water caused the difference in olivine fabric. Fabric strength of olivine gets weaker as the grain size reduced, and as a result calculated seismic properties for the two deformation stages reveal that P- and S-velocity anisotropies are significantly weaker in the mylonite. Microtextures and LPO data indicate that the deformation mechanism changed from dominant dislocation creep in spinel lherzolite to dislocation creep accompanied by grain-boundary sliding in mylonite. Shear localization in the mylonite appears to be originated from the grain size reduction through (1) enhanced dynamic recrystallization of olivine in the presence of water and (2) Zener pinning of clinopyroxene, or (3) by ultracommunition during the pseudotachylyte stage.

  9. Using Remote Sensing Techniques to Assess the Geologic Context of Olivine-Bearing Materials within Terra Sirenum, Mars

    NASA Astrophysics Data System (ADS)

    Anderson, M.; Osterloo, M. M.

    2015-12-01

    Understanding olivine-bearing materials in Terra Sirenum provides insight into the magmatic and hydrologic processes that shaped the Southern Highlands of Mars. Our study addresses two questions: "What is the geologic context of olivine compositions in the study area?" and "What does olivine abundance, composition, and geologic context suggest about the magmatic and weathering processes in our study area?" To answer these questions, we mapped olivine deposits within a region of Terra Sirenum using JMARS [1]. We used Thermal Emission Imaging System (THEMIS) data to map the extent of olivine deposits and to understand their degree of consolidation. To investigate olivine composition, we used the Thermal Emission Spectrometer (TES) global maps of Forsterite/Fayalite compositions [2]. We found that the olivine compositions vary from most iron-rich types (Fo01) to the most magnesium-rich (Fo91), with the vast majority identified as Fo68. The results of our study are consistent with those implied by the magma overturn model [3], which explains the compositional changes in Martian magmas over time. In addition, the extent of olivine-bearing deposits within our study area suggests that mechanical weathering (e.g., aeolian and gravity-driven processes) is more likely to dominate the sedimentary record in recent geologic time over water-driven processes. We will present our results, which detail the present-day surface geology of our study area in Terra Sirenum. Our results have implications for Martian magma evolution as well as the extent water has played in shaping the surface of the planet. [1] Gorelick, N., et al. (2003), Lunar and Planetary Science, XXXIV. [2] Koeppen, W.C., et al. (2008), Journal of Geophysical Research, 113, E002984. [3] Elkins-Tanton, L.T., et al. (2003), Meteorites & Planetary Science, 38, tb00013.

  10. Evidence of phase nucleation during olivine diffusion creep: a new perspective for mantle strain localization and Plate tectonics

    NASA Astrophysics Data System (ADS)

    Precigout, J.; Stunitz, H.; Le Breton, N.

    2015-12-01

    Mantle strain localization is of great importance for lithosphere dynamics, but the cause for this phenomenon still remains very elusive, particularly in conditions of the strong and ductile uppermost mantle. Based on Griggs-type experiments, we show here that strain localization arises from solution transfer at olivine-pyroxene interfaces while olivine deforms by low-temperature creep. Deforming olivine (70%) plus diopside (30%) aggregates at 900°C and 1.2 GPa in presence of water, these experiments produce typical ductile shear zones which develop during substantial drop of the sample strength. At these conditions, olivine deforms through low-temperature plasticity and weakens, partly due to dynamic recrystallization driven by grain boundary migration. However, although substantial, this weakening alone does not promote strain localization, which only occurs if secondary phases are present. Indeed, the presence of clinopyroxene (CPx) leads to the formation of a fine-grained olivine-CPx mixture (~0.1 micron grain size) that extends in thin layers from the tips of CPx. Because of phase mixing and grain growth inhibition that stabilize the extremely small grain size, these layers deform through grain-size-sensitive creep, promoting further weakening of the sample. Together with strain-induced olivine weakening, this mixture-related weakening acts as a critical process for strain to localize. Furthermore, the presence of mixture with fluid inclusions in cracks of CPx indicate that new olivine and CPx crystallize from a fluid phase, in favor of chemically driven solution transfer at CPx boundaries. Our findings thus emphasize solution transfer as a start-up process for strain localization, provided that olivine aggregates weaken during plastic flow, as documented for low-temperature creep.

  11. Characterization of olivine fabrics and mylonite in the presence of fluid and implications for seismic anisotropy and shear localization

    NASA Astrophysics Data System (ADS)

    Jung, Sejin; Jung, Haemyeong; Austrheim, Håkon

    2014-12-01

    The Lindås Nappe, Bergen Arc, is located in western Norway and displays two high-grade metamorphic structures. A Precambrian granulite facies foliation is transected by Caledonian fluid-induced eclogite-facies shear zones and pseudotachylytes. To understand how a superimposed tectonic event may influence olivine fabric and change seismic anisotropy, two lenses of spinel lherzolite were studied by scanning electron microscope (SEM) and electron back-scattered diffraction (EBSD) techniques. The granulite foliation of the surrounding anorthosite complex is displayed in ultramafic lenses as a modal variation in olivine, pyroxenes, and spinel, and the Caledonian eclogite-facies structure in the surrounding anorthosite gabbro is represented by thin (<1 cm) garnet-bearing ultramylonite zones. The olivine fabrics in the spinel bearing assemblage were E-type and B-type and a combination of A- and B-type lattice preferred orientations (LPOs). There was a change in olivine fabric from a combination of A- and B-type LPOs in the spinel bearing assemblage to B- and E-type LPOs in the garnet lherzolite mylonite zones. Fourier transform infrared (FTIR) spectroscopy analyses reveal that the water content of olivine in mylonite is much higher (approximately 600 ppm H/Si) than that in spinel lherzolite (approximately 350 ppm H/Si), indicating that water caused the difference in olivine fabric. Fabric strength of olivine gets weaker as the grain size reduced, and as a result, calculated seismic properties for the two deformation stages reveal that P- and S-velocity anisotropies are significantly weaker in the mylonite. Microtextures and LPO data indicate that the deformation mechanism changed from dominant dislocation creep in spinel lherzolite to dislocation creep accompanied by grain-boundary sliding in mylonite. Shear localization in the mylonite appears to be originated from the grain size reduction through (1) enhanced dynamic recrystallization of olivine in the presence of

  12. Laboratory Simulation of Space Weathering: ESR Measurements of Nanophase Metallic Iron in Laser-irradiated Olivine and Pyroxene Samples

    NASA Technical Reports Server (NTRS)

    Kurahashi, E.; Yamanaka, C.; Nakamura, K.; Sasaki, S.

    2003-01-01

    S-type asteroids are believed to be parent bodies of ordinary chondrites. Although both S-type asteroids and ordinary chondrites contain the same mineral assemblage, mainly olivine and pyroxene, the reflectance spectra of the asteroids exhibit more overall depletion (darkening) and reddening, and more weakening of absorption bands relative to the meteorites. This spectral mismatch is explained by space weathering process, where high-velocity dust particle impacts should change the optical properties of the uppermost regolith surface of asteroids. In order to simulate the space weathering, we irradiated nanosecond pulse laser beam onto pellet samples of olivine (8.97wt% FeO) and pyroxene (enstatite: 9.88wt% FeO, hypersthene: 16.70wt%). We got spectral changes in our samples similar to that by space weathering on asteroids and confirmed nanophase alpha-metallic iron particles, which were theoretically predicted, not only on olivine but also on pyroxene samples by Transmission Electron Microscopy (TEM). Nanophase metallic iron particles were widely scattered throughout the amorphous rims developed along the olivine grains, whereas they were embedded in aggregates of amorphous in enstatite samples. Recently, we also measured laser-irradiated samples by ESR (Electron Spin Resonance). Strong ESR