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Sample records for olivines limnpo4 lifepo4

  1. Formation and diffusion of vacancy-polaron complex in olivine-type LiMnPO4 and LiFePO4

    NASA Astrophysics Data System (ADS)

    Asari, Yusuke; Suwa, Yuji; Hamada, Tomoyuki

    2011-10-01

    Formation and diffusion of a vacancy-polaron complex in olivine-type cathode-active materials, namely, LiMPO4 (M = Fe, Mn), were theoretically investigated by using the first-principles density functional theory within a framework of GGA + U method. It is shown that a lithium vacancy and a corresponding hole-polaron form the complex at the fully lithiated limit owing to lattice distortion and Coulomb interaction between them. It is also shown that the formation energy of the complex in LiMnPO4 is 0.19 eV higher than that in LiFePO4, since a hole polaron in LiMnPO4 is not sufficiently relaxed. As a result, the nucleation rate of MnPO4 phase in LiMnPO4 is 10-3 times slower than that in LiFePO4 and represents the main difference between the kinetics in the initial stage of charging of the two olivine materials. It was also found that the activation energy of the complex diffusion is limited by vacancy hopping in LiMnPO4, while it is determined by both vacancy hopping and polaron hopping in LiFePO4. The activation energy in LiMnPO4, 0.38 eV, is comparable with that in LiFePO4, 0.42 eV. The calculated potential energy profile, showed that the minimum energy path of the diffusing lithium in LiMnPO4 has the same winding shape as that in LiFePO4.

  2. Dynamic solubility limits in nanosized olivine LiFePO4.

    PubMed

    Wagemaker, Marnix; Singh, Deepak P; Borghols, Wouter J H; Lafont, Ugo; Haverkate, Lucas; Peterson, Vanessa K; Mulder, Fokko M

    2011-07-01

    Because of its stability, nanosized olivine LiFePO(4) opens the door toward high-power Li-ion battery technology for large-scale applications as required for plug-in hybrid vehicles. Here, we reveal that the thermodynamics of first-order phase transitions in nanoinsertion materials is distinctly different from bulk materials as demonstrated by the decreasing miscibility gap that appears to be strongly dependent on the overall composition in LiFePO(4). In contrast to our common thermodynamic knowledge, that dictates solubility limits to be independent of the overall composition, combined neutron and X-ray diffraction reveals strongly varying solubility limits below particle sizes of 35 nm. A rationale is found based on modeling of the diffuse interface. Size confinement of the lithium concentration gradient, which exists at the phase boundary, competes with the in bulk energetically favorable compositions. Consequently, temperature and size diagrams of nanomaterials require complete reconsideration, being strongly dependent on the overall composition. This is vital knowledge for the future nanoarchitecturing of superior energy storage devices as the performance will heavily depend on the disclosed nanoionic properties. PMID:21598941

  3. 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.

  4. Coupling of Li motion and structural distortions in olivine LiMnPO4 from 7Li and 31P NMR

    NASA Astrophysics Data System (ADS)

    Rudisch, Christian; Grafe, Hans-Joachim; Geck, Jochen; Partzsch, Sven; Zimmermann, M. v.; Wizent, Nadja; Klingeler, Rüdiger; Büchner, Bernd

    2013-08-01

    We present a detailed 7Li- and 31P-NMR study on single crystalline LiMnPO4 in the paramagnetic and antiferromagnetic phase (AFM, TN˜34 K). This allows us to determine the spin directions in the field-induced spin-flop phase. In addition, the anisotropic dipolar hyperfine coupling tensor of the 7Li and 31P nuclei is also fully determined by orientation and temperature-dependent NMR experiments and compared to the calculated values from crystal structure data. Deviations of the experimental values from the theoretical ones are discussed in terms of Mn disorder which is induced by Li disorder. In fact, the disorder in the Mn sublattice is directly revealed by diffuse x-ray scattering data. The present results provide experimental evidence for the Li diffusion strongly coupling to structural distortions within the MnPO4 host, which is expected to significantly affect the Li mobility as well as the performance of batteries based on this material.

  5. What Happens to LiMnPO4 upon Chemical Delithiation?

    PubMed

    Huang, Yiqing; Chernova, Natasha A; Yin, Qiyue; Wang, Qi; Quackenbush, Nicholas F; Leskes, Michal; Fang, Jin; Omenya, Fredrick; Zhang, Ruibo; Wahila, Matthew J; Piper, Louis F J; Zhou, Guangwen; Grey, Clare P; Whittingham, M Stanley

    2016-05-01

    Olivine MnPO4 is the delithiated phase of the lithium-ion-battery cathode (positive electrode) material LiMnPO4, which is formed at the end of charge. This phase is metastable under ambient conditions and can only be produced by delithiation of LiMnPO4. We have revealed the manganese dissolution phenomenon during chemical delithiation of LiMnPO4, which causes amorphization of olivine MnPO4. The properties of crystalline MnPO4 obtained from carbon-coated LiMnPO4 and of the amorphous product resulting from delithiation of pure LiMnPO4 were studied and compared. The phosphorus-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P2O7 from NMR, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analysis. The thermal stability of MnPO4 is significantly higher under high vacuum than at ambient condition, which is shown to be related to surface water removal. PMID:27065434

  6. 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.

  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. Ultralong Lifespan and Ultrafast Li Storage: Single-Crystal LiFePO4 Nanomeshes.

    PubMed

    Zhang, Yan; Zhang, Hui Juan; Feng, Yang Yang; Fang, Ling; Wang, Yu

    2016-01-27

    A novel LiFePO4 material, in the shape of a nanomesh, has been rationally designed and synthesized based on the low crystal-mismatch strategy. The LiFePO4 nanomesh possesses several advantages in morphology and crystal structure, including a mesoporous structure, its crystal orientation that is along the [010] direction, and a shortened Li-ion diffusion path. These properties are favorable for their application as cathode in Li-ion batteries, as these will accelerate the Li-ion diffusion rate, improve the Li-ion exchange between the LiFePO4 nanomesh and the electrolyte, and reduce the Li-ion capacitive behavior during Li intercalation. So the LiFePO4 nanomesh exhibits a high specific capacity, enhanced rate capability, and strengthened cyclability. The method developed here can also be extended to other similar systems, for instance, LiMnPO4 , LiCoPO4 , and LiNiPO4 , and may find more applications in the designed synthesis of functional materials. PMID:26643716

  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. Synthesis and Electrochemical Properties of LiFePO4/C for Lithium Ion Batteries.

    PubMed

    Gao, Hong; Wang, Jiazhao; Yin, Shengyu; Zheng, Hao; Wang, Shengfu; Feng, Chuanqi; Wang, Shiquan

    2015-03-01

    LiFePO4/C was prepared through a facile rheological phase reaction method by using Fe3(PO4)2, Li3PO4 · 8H2O, and glucose as reactants. The LiFePO4/C samples were characterized by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The electrochemical properties of the samples were investigated. The results show that the LiFePO4/C samples have single-phase olivine-type structure, and their particles feature a spherical shape. The carbon coating on the particles of LiFePO4 is about 1.8% of the LiFePO4/C by weight. The particle size was distributed from 0.2 to 1 µm. The initial discharge capacity of LiFePO4/C reached 154 mA h/g at 0.1 C. The retained discharge capacity of LiFePO4/C was 152.9 mA h g(-1) after 50 cycles. The LiFePO4/C also showed better cycling performance than that of the bare LiPeO4 at a higher charge/discharge rate (1 C). The LIFePO4/C prepared in this way could be a promising cathode material for lithium ion battery application. PMID:26413648

  12. Optical Properties and Electrochemical Performance of LiFePO4 Thin Films Deposited on Transparent Current Collectors.

    PubMed

    Lee, HyunSeok; Yim, Haena; Kim, Kwang-Bum; Choi, Ji-Won

    2015-11-01

    LiFePO4 thin film cathodes are deposited on various transparent conducting oxide thin films on glass, which are used as cathode current collectors. The XRD patterns show that the thin films have the phase of LiFePO4 with an ordered olivine structure indexed to the orthorhombic Pmna space group. LiFePO4 thin film deposited on various TCO glass substrates exhibits transmittance of about 53%. The initial specific discharge capacities of LiFePO4 thin films are 25.0 μAh/cm2 x μm on FTO, 33.0 μAh/cm2 x μm on ITO, and 13.0 μAh/cm2 x μm on AZO coated glass substrates. Interestingly, the retention capacities of LiFePO4 thin films are 76.0% on FTO, 31.2% on ITO, and 37.7% on AZO coated glass substrates at 20th cycle. The initial specific discharge capacity of the LiFePO4/FTO electrode is slightly lower, but the discharge capacities of the LiFePO4/FTO electrode relatively decrease less than those of the others such as LiFePO4/ITO and LiFePO4/AZO with cycling. The results reported here provide the high transparency of LiFePO4 thin films cathode materials and the good candidate as FTO current collector of the LiFePO4 thin film cathode of transparent thin film rechargeable batteries due to its high transparency and cyclic retention. PMID:26726564

  13. First-Principles Investigation of Li Intercalation Kinetics in Phospho-Olivines

    NASA Astrophysics Data System (ADS)

    Malik, Rahul

    This thesis focuses broadly on characterizing and understanding the Li intercalation mechanism in phospho-olivines, namely LiFePO 4 and Li(Fe,Mn)PO4, using first-principles calculations. Currently Li-ion battery technology is critically relied upon for the operation of electrified vehicles, but further improvements mainly in cathode performance are required to ensure widespread adoption, which in itself requires learning from existing commercial cathode chemistries. LiFePO4 is presently used in commercial Li-ion batteries, known for its rapid charge and discharge capability but with underwhelming energy density. This motivates the three central research efforts presented herein. First, we investigate the modified phase diagram and electrochemical properties of mixed olivines, such as Li(Fe,Mn)PO4, which offer improved theoretical energy density over LiFePO4 (due to the higher redox voltage associated with Mn2+/Mn3+). The Lix(Fe1-yMny)PO4 phase diagram is constructed by Monte Carlo simulation on a cluster expansion Hamiltonian parametrized by first-principles determined energies. Deviations from the equilibrium phase behavior and voltages of pure LiFePO4 and LiMnPO 4 are analyzed and discussed to good agreement with experimental observations. Second, we address why LiFePO4 exhibits superior rate performance strictly when the active particle size is brought down to the nano-scale. By considering the presence of immobile point defects residing in the 1D Li diffusion path, specifically by calculating from first principles both defect formation energies and Li migration barriers in the vicinity of likely defects, the Li diffusivity is recalculated and is found to strongly vary with particle size. At small particle sizes, the contribution from defects is small, and fast 1D Li diffusion is accessible. However, at larger particle sizes (microm scale and above) the contribution from defects is much larger. Not only is Li transport impeded, but it is also less anisotropic in

  14. Microwave synthesis of molybdenum doped LiFePO4/C and its electrochemical studies.

    PubMed

    Naik, Amol; P, Sajan C

    2016-05-10

    A Mo-doped LiFePO4 composite was prepared successfully from an iron carbonyl complex by adopting a facile and rapid microwave assisted solid state method. The evolution of gases from the iron precursor produces a highly porous product. The formation and substitution of Mo in LiFePO4 were confirmed by X-ray diffraction; surface analysis was carried out by scanning electron microscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical properties of the substituted LiFePO4 were examined by cyclic voltammetry, electrochemical impedance spectroscopy and by recording charge-discharge cycles. It was observed that the as prepared composites consisted of a single phase orthorhombic olivine-type structure, where Mo(6+) was successfully introduced into the M2(Fe) sites. Incorporation of supervalent Mo(6+) introduced Li(+) ion vacancies in LiFePO4. The synthesized material facilitated lithium ion diffusion during charging/discharging due to the charge compensation effect and porosity. The battery performance studies showed that LiMo0.05Fe0.095PO4 exhibited a maximum capacity of 169.7 mA h g(-1) at 0.1 C current density, with admirable stability retention. Even at higher current densities, the retention of the specific capacity was exceptional. PMID:27071463

  15. 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.

  16. Synthesis of a LiFePO4/C cathode material by using a high-energy nano mill

    NASA Astrophysics Data System (ADS)

    Islam, Mobinul; Yoon, Man-Soon; Ur, Soon-Chul

    2015-07-01

    Olivine lithium iron phosphate (LiFePO4) is a promising cathode material for Li-ion battery. A temperature around 700 - 800 ℃ is generally required to prepare LiFePO4 powder with good crystallinity. The LiFePO4 materials are synthesized via a solid-state method by using a highenergy nano mill (HENM). The conventional ball-milling process is also conducted for the same material for a comparative study. The effect of the precursor's mixing processes on the synthesis temperature of LiFePO4 is investigated in this study. The required reaction temperature of LiFePO4 is 432 ℃ for the HENM process and 480 ℃ for the ball-mill process as found from the differential scanning calorimetry (DSC) results. The HENM process improves the reaction activity and the homogeneity of the materials used throughout process and lowers the reaction temperature as compared with the conventional ball-mill process. The milled powders are characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The sample synthesized by using the HENM process exhibits a discharge capacity of 136 mAhg -1 at 0.1 C rate. The results in this study indicate that the HENM process is a substantial and promising process for LiFePO4 cathode preparation owing to its short fabrication time and ability to improve the reaction condition. A HENM can be used to promote formation of LiFePO4 at lower temperatures.

  17. Rapid Polyol-Assisted Microwave Synthesis of Nanocrystalline LiFePO4/C Cathode for Lithium-Ion Batteries.

    PubMed

    Paul, Baboo Joseph; Gim, Jihyeon; Baek, Sora; Kang, Jungwon; Song, Jinju; Kim, Sungjin; Kim, Jaekook

    2015-08-01

    Nanocrystalline LiFePO4/C has been synthesized under a very short period of time (90 sec) using a polyol-assisted microwave heating synthesis technique. The X-ray diffraction (XRD) data indicates that the rapidly synthesized materials correspond to phase pure olivine. Post-annealing of the as-prepared sample at 600 °C in argon atmosphere yields highly crystalline LiFePO4/C. The morphology of the samples studied using scanning electron microscopy (SEM) reveals the presence of secondary particles formed from aggregation of primary particles in the range of 30-50 nm. Transmission electron microscopy (TEM) images reveal a thin carbon layer coating on the surface of the primary particle. The charge/discharge studies indicate that the as-prepared and annealed LiFePO4/C samples delivered initial discharge capacities of 126 and 160 mA h g-1, respectively, with good capacity retentions at 0.05 mA cm-2 current densities. The post-annealing process indeed improves the crystallinity of the LiFePO4 nanocrystals, which enhances the electrode performance of LiFePO4/C. PMID:26369219

  18. 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.

  19. Effects of Ag-embedment on electronic and ionic conductivities of LiMnPO4 and its performance as a cathode for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Kug-Seung; Lee, Kyung Jae; Kang, Yun Sik; Shin, Tae Joo; Sung, Yung-Eun; Ahn, Docheon

    2015-08-01

    An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (~26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP cathode exhibited outstanding electrochemical performances (92 mA h g-1 at 10 C) versus lithium.An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (~26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP

  20. Analysis of optimization processses for solid state fabrication of olivine cathode materials

    NASA Astrophysics Data System (ADS)

    Oladimeji, Charles

    Lithium ion battery discovered since the 1980s has become pivotal to our energy needs. With the need for a shift to renewable energy and increased use of portable devices, energy storage has become a very important aspect of modern day life and technology. In the thesis, optimization techniques for solid state calcination of lithium olivine batteries are characterized and analyzed. A brief introduction into lithium ion battery is discussed, the chemistry and physics of the materials is studied in details. Emphasis is placed on the olivine structure, industrially utilized synthesis method and the performance of olivine lithium ion batteries are also discussed in details. Olivine structure LiFePO4 (LFP) was synthesized via solid state processes, using Li2CO3, NH4H 2PO4 and FeC2O4˙H2O and C12H22O11 as precursor materials. The effects of calendaring in terms of charge/discharge capacity, cycle life performance, surface morphology, and ac impedance was analyzed. The resulting LFP electrode was divided in part, Part A was left as is and Part B was calendared. The calendared electrode exhibited lower impedance under electrochemical impedance test. The calendared electrode also exhibited a higher discharge capacity of about 130 mAh/g at 0.1C compared to the as-is electrode with discharge capacity of about 120mAh/g. Olivine structure LiMnPO4 (LMP) was also synthesized via solid state processes, using Li2CO3, NH4H 2PO4, MnCO3 and C12H22O 11 as precursor materials. Comparison of the carbon addition process was done by adding sucrose to the initial precursor mix and carbon black at the later stages of fabrication. The 3 step carbon addition exhibited the highest specific capacity of about 72mAh/g, 1 step carbon addition possessed the least capacity of about 45mAh/g, while the 2 step process had a capacity of about 65mA/g.

  1. LiMnPO4 Nanoplate Grown via Solid-State Reaction in Molten Hydrocarbon for Li-ion Battery Cathode

    SciTech Connect

    Choi, Daiwon; Wang, Donghai; Bae, In-Tae; Xiao, Jie; Nie, Zimin; Wang, Wei; Viswanathan, Vilayanur V.; Lee, Yun Jung; Zhang, Jiguang; Graff, Gordon L.; Yang, Zhenguo; Liu, Jun

    2010-08-11

    Electrochemically active LiMnPO4 nanoplates have been synthesized via novel single step solid state reaction in molten hydrocarbon. The LiMnPO4 prepared show unique porous nanoplate shape ~50nm in thickness with highly preferred crystallographic orientation. The reversible cycling of carbon coated LiMnPO4 show flat potential at 4.1 V vs. Li with specific capacity reaching up to 168mAh/g and excellent cycling performance using only galvanostatic charging / discharging mode.

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

    PubMed

    Wu, Jiaxiong; Cai, Wei; Shang, Guangyi

    2016-12-01

    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. PMID:27117633

  3. 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.

  4. 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.

  5. Effects of Ag-embedment on electronic and ionic conductivities of LiMnPO4 and its performance as a cathode for lithium-ion batteries.

    PubMed

    Lee, Kug-Seung; Lee, Kyung Jae; Kang, Yun Sik; Shin, Tae Joo; Sung, Yung-Eun; Ahn, Docheon

    2015-09-01

    An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (∼26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP cathode exhibited outstanding electrochemical performances (92 mA h g(-1) at 10 C) versus lithium. PMID:26186268

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. Enhanced rate performance of LiFePO4/C by co-doping titanium and vanadium

    NASA Astrophysics Data System (ADS)

    Long, Yun-Fei; Su, Jing; Cui, Xiao-Ru; Lv, Xiao-Yan; Wen, Yan-Xuan

    2015-10-01

    V and Ti co-doped LiFePO4/C composites were synthesized by a wet milling assisted carbothermal reduction technology. The structure, morphology and electrochemical performance of the samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), magnetic susceptibility, positron annihilation lifetime spectra (PAS), scanning electron microscope (SEM), charge/discharge tests, electrochemical impedance spectroscopy (EIS) and cyclic voltammograms (CV). The results showed that the V and Ti co-doped samples kept the olivine structure of LiFePO4, but the synergistic effects between V3+ and Ti4+ in the lattice can increase the disorder degree of the lattice and create Li+ vacancies in LiFePO4/C, thus improve electronic conductivity and Li+ diffusion coefficient. LiV0.069Ti0.025Fe0.905PO4/C delivers an initial discharge capacity of 144.1 mAh g-1 with a capacity retention ratio of 99.4%, 96.3% and 93.6% after 100, 200 and 300 cycles at 10C, respectively. Remarkably, it still gives a high discharge capacity of 124.8 mAh g-1 even at a high rate of 20C.

  11. 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.

  12. 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.

  13. 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}.

  14. 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. PMID:26799094

  15. 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

  16. Ultrathin carbon nanopainting of LiFePO4 by oxidative surface polymerization of dopamine

    NASA Astrophysics Data System (ADS)

    Ding, Bo; Tang, Wei Chin; Ji, Ge; Ma, Yue; Xiao, Pengfei; Lu, Li; Lee, Jim Yang

    2014-11-01

    The common strategy to address the low electronic conductivity of LiFePO4 is to downsize LiFePO4 and to coat the nanocrystal with conductive carbon film. The major issues with existing carbon coating techniques are thickness and quality control. This paper reports a facile carbon coating method which can provide ultrathin, uniform and fully encapsulating carbon coating on LiFePO4. This coating method capitalizes on the redox chemistry of surface Fe3+ on solvothermally synthesized LiFePO4 nanocrystal, to deposit uniform thin films of polydopamine films. The polymer film is easily carbonized into ultrathin carbon film. The carbon coated LiFePO4 exhibits very high rate performance (143 mAh g-1 at current density of 1700 mA g-1) with excellent capacity retention.

  17. 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.

  18. 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

  19. 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. PMID:24287590

  20. Electrochemical performance of patterned LiFePO4 nano-electrode with a pristine amorphous layer

    NASA Astrophysics Data System (ADS)

    Wang, Mao; Zhang, Wei; Liu, Yihang; Yang, Yong; Wang, Chunsheng; Wang, Yuan

    2014-04-01

    A patterned LiFePO4 nanorod with a pristine amorphous LiFePO4 surface layer was fabricated by controlling the temperature gradient from the interior to the exterior layer in high-temperature annealing process through designing hierarchical multilayer electrode structure. The three dimensional patterned LiFePO4 nanorods were prepared using tobacco mosaic virus nanoforest arrays. The results indicate that the nano-electrodes nearly reached the theoretical capacity at a very low C rate even without conductive coatings. The amorphous LiFePO4 can fast transport the Li-ion to inside crystal LiFePO4, thus enhancing the rate capability.

  1. Rate-dependent, Li-ion insertion/deinsertion behavior of LiFePO4 cathodes in commercial 18650 LiFePO4 cells.

    PubMed

    Liu, Qi; He, Hao; Li, Zhe-Fei; Liu, Yadong; Ren, Yang; Lu, Wenquan; Lu, Jun; Stach, Eric A; Xie, Jian

    2014-03-12

    We have performed operando synchrotron high-energy X-ray diffraction (XRD) to obtain nonintrusive, real-time monitoring of the dynamic chemical and structural changes in commercial 18650 LiFePO4/C cells under realistic cycling conditions. The results indicate a nonequilibrium lithium insertion and extraction in the LiFePO4 cathode, with neither the LiFePO4 phase nor the FePO4 phase maintaining a static composition during lithium insertion/extraction. On the basis of our observations, we propose that the LiFePO4 cathode simultaneously experiences both a two-phase reaction mechanism and a dual-phase solid-solution reaction mechanism over the entire range of the flat voltage plateau, with this dual-phase solid-solution behavior being strongly dependent on charge/discharge rates. The proposed dual-phase solid-solution mechanism may explain the remarkable rate capability of LiFePO4 in commercial cells. PMID:24521163

  2. Effect of conductive additives in LiFePO4 cathode for lithium-ion batteries

    SciTech Connect

    Shim, J.; Guerfi, A.; Zaghib, K.; Striebel, K.A.

    2003-11-25

    The electrochemical properties of LiFePO4 cathodes with different carbon contents were studied to find out the role of carbon as conductive additive. LiFePO4 cathodes containing from 0 percent to 12 percent of conductive additive (carbon black or mixture of carbon black and graphite) were cycled at different C rates. The capacity of LiFePO4 cathode increased, as conductive additive content increased. Carbon increased the utilization of active material and the electrical conductivity of electrode, but decreased volumetric capacity of electrode.

  3. Structure and performance of LiFePO4 cathode materials: A review

    NASA Astrophysics Data System (ADS)

    Zhang, Wei-Jun

    2011-03-01

    LiFePO4 has been considered a promising battery material in electric vehicles. However, there are still a number of technical challenges to overcome before its wide-spread applications. In this article, the structure and electrochemical performance of LiFePO4 are reviewed in light of the major technical requirements for EV batteries. The rate capability, capacity density, cyclic life and low-temperature performance of various LiFePO4 materials are described. The major factors affecting these properties are discussed, which include particle size, doping, carbon coating, conductive carbon loading and synthesis techniques. Important future research for science and engineering is suggested.

  4. [100]-Oriented LiFePO4 Nanoflakes toward High Rate Li-Ion Battery Cathode.

    PubMed

    Li, Zhaojin; Peng, Zhenzhen; Zhang, Hui; Hu, Tao; Hu, Minmin; Zhu, Kongjun; Wang, Xiaohui

    2016-01-13

    [100] is believed to be a tough diffusion direction for Li(+) in LiFePO4, leading to the belief that the rate performance of [100]-oriented LiFePO4 is poor. Here we report the fabrication of 12 nm-thick [100]-oriented LiFePO4 nanoflakes by a simple one-pot solvothermal method. The nanoflakes exhibit unexpectedly excellent electrochemical performance, in stark contrast to what was previously believed. Such an exceptional result is attributed to a decreased thermodynamic transformation barrier height (Δμb) associated with increased active population. PMID:26694590

  5. 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.

  6. Probing the failure mechanism of nanoscale LiFePO4 for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Gu, Meng; Shi, Wei; Zheng, Jianming; Yan, Pengfei; Zhang, Ji-guang; Wang, Chongmin

    2015-05-01

    LiFePO4 is a high power rate cathode material for lithium ion battery and shows remarkable capacity retention, featuring a 91% capacity retention after 3300 cycles. In this work, we use high-resolution transmission electron microscopy and electron energy loss spectroscopy to study the gradual capacity fading mechanism of LiFePO4 materials. We found that upon prolonged electrochemical cycling of the battery, the LiFePO4 cathode shows surface amorphization and loss of oxygen species, which directly contribute to the gradual capacity fading of the battery. The finding can guide the design and improvement of LiFePO4 cathode for high-energy and high-power rechargeable battery for electric transportation.

  7. 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.

  8. 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.

  9. 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

  10. Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing.

    PubMed

    Li, Jianlin; Armstrong, Beth L; Kiggans, Jim; Daniel, Claus; Wood, David L

    2012-02-28

    Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance. PMID:22292836

  11. 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

    2015-01-01

    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

  12. 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.

  13. Synthesis, non-isothermal kinetic and thermodynamic studies of the formation of LiMnPO4 from NH4MnPO4·H2O precursor

    NASA Astrophysics Data System (ADS)

    Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

    2014-06-01

    NH4MnPO4·H2O was successfully synthesized by precipitating method. The LiMnPO4 was successfully generated through solid state reaction between synthesized NH4MnPO4·H2O precursor and Li2CO3. The morphologies were observed to depend on the reaction temperatures. The thermal decomposition of NH4MnPO4·H2O and the formation process of LiMnPO4 were confirmed by TG/DTG/DTA, FTIR, AAS/AES, XRD and SEM methods. The average crystallite size of NH4MnPO4·H2O, Mn2P2O7 and LiMnPO4 were found to be around 51.2, 44.9 and 48.1 nm, respectively. The non-isothermal kinetic parameters (kinetic triplet: Eα, A, g(α)) of the formation process of LiMnPO4 were evaluated from TG data by using Ozawa-Flynn-Wall and Kissinger-Akahira-Sunose methods. The iterative methods of both equations were carried out to determine the exact values of Eα. The Coats-Redfern equation and kinetic compensation effects were successfully applied to confirm the activation energy and the most probable mechanism functions of the formation of LiMnPO4. The thermodynamic functions (ΔH≠, ΔS≠, ΔG≠) of the transition state complexes of the formation of LiMnPO4 were calculated from the kinetic parameters for the first time.

  14. 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.

  15. Synthesis of LiFePO4/Pani/C composite as a cathode material for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Rahayu, Iman; Hidayat, Sahrul; Aryadi, Lutfi

    2016-02-01

    In recent years, LiFePO4 studied intensively as a cathode material for Li-ion batteries because of high theoretical capacity, stability, and environmental friendly. However, its low intrinsic electronic conductivity. One way to improve its conductivity is addition of conductive material. Polyaniline (PANI) is one of the conductive polymer materials that widely studied because its unique physical and chemical properties which can be an insulator and conductor by doping-dedoping processes and has large potential application. The purpose of this research is to improve the conductivity of LiFePO4 with conductive polymer PANI. The method is performed by the addition of LiFePO4 during the polymerization process to form LiFePO4 polyaniline then added to the C-PANI with the addition of mass percent variation of 5%, 10%, 15%, 20% form-LiFePO4 composite PANI-C. In LiFePO4 added during polymerization PANI provide a smooth surface profile after composited with the carbon to LiFePO4-PANI-C compared to LiFePO4-C. LiFePO4-PANI-C composite provided higher conductivity is 18.45×10-4 S/cm compared to LiFePO4-C is 10.48×10-4 S/cm at 20% addition of carbon. This is due to PANI in LiFePO4 is added to the polyaniline polymerization process can act as a conductive adhesive to glue between carbon and LiFePO4.

  16. Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

    2016-01-01

    Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. Structural and Electrical Properties of Lithium-Ion Rechargeable Battery Using the LiFePO4/Carbon Cathode Material.

    PubMed

    Kim, Young-Sung; Jeoung, Tae-Hoon; Nam, Sung-Pill; Lee, Seung-Hwan; Kim, Jea-Chul; Lee, Sung-Gap

    2015-03-01

    LiFePO4/C composite powder as cathode material and graphite powder as anode material for Li-ion batteries were synthesized by using the sol-gel method. An electrochemical improvement of LiFePO4 materials has been achieved by adding polyvinyl alcohol as a carbon source into as-prepared materials. The samples were characterized by elemental analysis (EA), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-EM). The chemical composition of LiFePO4/C powders was in a good agreement with that of the starting solution. The capacity loss after 500 cycles of LiFePO4/C cell is 11.1% in room temperature. These superior electrochemical properties show that LiFePO4/C composite materials are promising candidates as cathode materials. PMID:26413683

  3. 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.

  4. Mössbauer study on LiFePO4 cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Hannoyer, B.; Prince, A. A. M.; Jean, M.; Liu, R. S.; Wang, G. X.

    2006-01-01

    Crystalline LiFePO4 has been synthesized using solid-state, spray pyrolysis, and wet chemical methods. The crystal parameters were obtained from Rietveld’s refinement methods of the X-ray diffraction patterns. A detailed investigation of the Fe valency carried out using Mössbauer spectroscopy at room temperature indicates that Fe is predominantly present in its bivalent state.

  5. Mössbauer study on LiFePO4 cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Hannoyer, B.; Prince, A. A. M.; Jean, M.; Liu, R. S.; Wang, G. X.

    Crystalline LiFePO4 has been synthesized using solid-state, spray pyrolysis, and wet chemical methods. The crystal parameters were obtained from Rietveld's refinement methods of the X-ray diffraction patterns. A detailed investigation of the Fe valency carried out using Mössbauer spectroscopy at room temperature indicates that Fe is predominantly present in its bivalent state.

  6. 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.

  7. 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.

  8. The development of low cost LiFePO4-based high power lithium-ion batteries

    SciTech Connect

    Shim, Joongpyo; Sierra, Azucena; Striebel, Kathryn A.

    2003-11-25

    The cycling performance of low-cost LiFePO4-based high-power lithium-ion cells was investigated and the components were analyzed after cycling to determine capacity fade mechanisms. Pouch type LiFePO4/natural graphite cells were assembled and evaluated by constant C/2 cycling, pulse-power and impedance measurements. From post-test electrochemical analysis after cycling, active materials, LiFePO4 and natural graphite, showed no degradation structurally or electrochemically. The main reasons for the capacity fade of cell were lithium inventory loss by side reaction and possible lithium deposition on the anode.

  9. A novel nano structured LiFePO4/C composite as cathode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Huang; Liu, Dong; Qian, Xiuzhen; Zhao, Chongjun; Xu, Yunlong

    2014-03-01

    A novel network LiFePO4/C composite was prepared by mixing precursor solution with carbon aerogel (CA) via a simple solution impregnation method, characterized by XRD, SEM, EDS and electrochemical analysis. The results revealed that the LiFePO4 nanowire forming on the ektexine of CA intertwined with LiFePO4/CA particles and formed a special web structure. The initial discharge capacity was improved to be 139.3 mAh g-1 at 10 C and the capacity retention is near 100% after 50 cycles. The web structure could improve electron transport and electrochemical activity effectively.

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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. PMID:26666453

  17. 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

  18. 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

  19. Preparation of V-Doped LiFePO4/C as the Optimized Cathode Material for Lithium Ion Batteries.

    PubMed

    Sun, Pingping; Zhang, Haiyang; Shen, Kai; Fan, Qi; Xu, Qingyu

    2015-04-01

    LiFe1-x,Vx,PO4/C composites were synthesized by solid state reaction. The effect of carbon coating and V doping on the performance of LiFePO4 has been systematically investigated by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), charge/discharge and cyclic voltammetry (CV) measurement. The results show that carbon coating and proper amount of V incorporation do not significantly change the host crystal structure of LiFePO4, while the electrochemical performance of LiFePO4 can be significantly improved. Particularly, the LiFe0.96V0.04PO4/C exhibits the best performance with a specific discharge capacity of 105.5 mA h/g at 5.0 C, 90.3 mA h/g at 10 C and 66.7 mA h/g at 30 C with stable cycle performance, which is significantly improved compared with the pure LiFePO4/C. The cyclic voltammograms result reveals that V doping could decrease the resistance of LiFePO4/C composite electrode drastically and improve its reversibility. PMID:26353479

  20. 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.

  1. 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.

  2. Electrochemical and kinetic studies of ultrafast laser structured LiFePO4 electrodes

    NASA Astrophysics Data System (ADS)

    Mangang, M.; Gotcu-Freis, P.; Seifert, H. J.; Pfleging, W.

    2015-03-01

    Due to a growing demand of cost-efficient lithium-ion batteries with an increased energy and power density as well as an increased life-time, the focus is set on intercalation cathode materials like LiFePO4. It has a high practical capacity, is environmentally friendly and has low material costs. However, its low electrical conductivity and low ionic diffusivity are major drawbacks for its use in electrochemical storage devices or electric vehicles. By adding conductive agents, the electrical conductivity can be enhanced. By increasing the surface of the cathode material which is in direct contact with the liquid electrolyte the lithium-ion diffusion kinetics can be improved. A new approach to increase the surface of the active material without changing the active particle packing density or the weight proportion of carbon black is the laser-assisted generation of 3D surface structures in electrode materials. In this work, ultrafast laser radiation was used to create a defined surface structure in LiFePO4 electrodes. It was shown that by using ultrashort laser pulses instead of nanosecond laser pulses, the ablation efficiency could be significantly increased. Furthermore, melting and debris formation were reduced. To investigate the diffusion kinetics, electrochemical methods such as cyclic voltammetry and galvanostatic intermittent titration technique were applied. It could be shown that due to a laser generated 3D structure, the lithium-ion diffusion kinetic, the capacity retention and cell life-time can be significantly improved.

  3. Redirected charge transport arising from diazonium grafting of carbon coated LiFePO4.

    PubMed

    Madec, L; Seid, K A; Badot, J-C; Humbert, B; Moreau, P; Dubrunfaut, O; Lestriez, B; Guyomard, D; Gaubicher, J

    2014-11-01

    The morphological and the electrical properties of carbon coated LiFePO4 (LFPC) active material functionalized by 4-ethynylbenzene tetrafluoroboratediazonium salt were investigated. For this purpose, FTIR, Raman, XPS, High Resolution Transmission Electron Microscopy (HRTEM) and Broadband Dielectric Spectroscopy (BDS) were considered. Electronic conductivities of LFPC samples at room temperature were found to decrease in a large frequency range upon simple immersion in polar solvents and to decrease further upon functionalization. Due to their high dipole moment, strongly physisorbed molecules detected by XPS likely add barriers to electron hopping. Significant alteration of the carbon coating conductivity was only observed, however, upon functionalization. This effect is most presumably associated with an increase in the sp(3) content determined by Raman spectroscopy, which is a strong indication of the formation of a covalent bond between the organic layer and the carbon coating. In this case, the electron flux appears to be redirected and relayed by short-range (intra chain) and long-range (inter chain) electron transport through molecular oligomers anchored at the LFPC surface. The latter are controlled by tunnelling and slightly activated hopping, which enable higher conductivity at low temperature (T < 250 K). Alteration of the electron transport within the carbon coating also allows detection of a relaxation phenomenon that corresponds to small polaron hopping in bulk LiFePO4. XPS and HRTEM images allow a clear correlation of these findings with the island type oligomeric structure of grafted molecules. PMID:25234701

  4. 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.

  5. 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.

  6. Emergence of Metallic Properties at LiFePO4 Surfaces and LiFePO4/Li2S Interfaces: An Ab Initio Study.

    PubMed

    Timoshevskii, Vladimir; Feng, Zimin; Bevan, Kirk H; Zaghib, Karim

    2015-08-26

    The atomic and electronic structures of the LiFePO4 (LFP) surface, both bare and reconstructed upon possible oxygenation, are theoretically studied by ab initio methods. On the basis of total energy calculations, the atomic structure of the oxygenated surface is proposed, and the effect of surface reconstruction on the electronic properties of the surface is clarified. While bare LFP(010) surface is insulating, adsorption of oxygen leads to the emergence of semimetallic behavior by inducing the conducting states in the band gap of the system. The physical origin of these conducting states is investigated. We further demonstrate that deposition of Li2S layers on top of oxygenated LFP(010) surface leads to the formation of additional conducting hole states in the first layer of Li2S surface because of the charge transfer from sulfur p-states to the gap states of LFP surface. This demonstrates that oxygenated LFP surface not only provides conducting layers itself, but also induces conducting channels in the top layer of Li2S. These results help to achieve further understanding of potential role of LFP particles in improving the performance of Li-S batteries through emergent interface conductivity. PMID:26237114

  7. Tailored surface structure of LiFePO4/C nanofibers by phosphidation and their electrochemical superiority for lithium rechargeable batteries.

    PubMed

    Lee, Yoon Cheol; Han, Dong-Wook; Park, Mihui; Jo, Mi Ru; Kang, Seung Ho; Lee, Ju Kyung; Kang, Yong-Mook

    2014-06-25

    We offer a brand new strategy for enhancing Li ion transport at the surface of LiFePO4/C nanofibers through noble Li ion conducting pathways built along reduced carbon webs by phosphorus. Pristine LiFePO4/C nanofibers composed of 1-dimensional (1D) LiFePO4 nanofibers with thick carbon coating layers on the surfaces of the nanofibers were prepared by the electrospinning technique. These dense and thick carbon layers prevented not only electrolyte penetration into the inner LiFePO4 nanofibers but also facile Li ion transport at the electrode/electrolyte interface. In contrast, the existing strong interactions between the carbon and oxygen atoms on the surface of the pristine LiFePO4/C nanofibers were weakened or partly broken by the adhesion of phosphorus, thereby improving Li ion migration through the thick carbon layers on the surfaces of the LiFePO4 nanofibers. As a result, the phosphidated LiFePO4/C nanofibers have a higher initial discharge capacity and a greatly improved rate capability when compared with pristine LiFePO4/C nanofibers. Our findings of high Li ion transport induced by phosphidation can be widely applied to other carbon-coated electrode materials. PMID:24786736

  8. Experimental and numerical study of phase transition of LiFePO 4 material in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Siddique, Md Noor E. Alam

    Phase transition behavior of LiFePO4 material has been studied in this work. During electrochemical charge/discharge processes, LiFePO 4 transforms into FePO4 and this electrochemically driven phase transition of the two-phase system results in a potential plateau in a battery discharge curve. Besides, battery performance, especially under high rates, depends critically on this two-phase transition. However, this phase transition mechanism in the LiFePO4 crystal structure has yet not been understood in details. Developing better understanding is essential for designing high performing, safe and stable batteries. Currently available phase transition models for LiFePO4, such as the classical `core-shrinking model' and recently the `domino cascade model', have shed lights on the phase transition mechanism, however, with somewhat contradicting conclusions. The former predicted a continuous phase transition between LiFePO4 and FePO4 within an individual particle. In contrast, the latter, based on the fact of anisotropic diffusion of Li, provided a microscopically heterogeneous picture of phase transition: phase transition is abrupt, and de-lithiated and lithiated particles co-exist in a battery electrode. To achieve a better understanding of the two-phase transition phenomena, two specially designed sophisticated methods, i.e., in-situ Raman spectroscopy and in-situ X-ray Diffraction (XRD), have been developed in this work. The particle level phase transition of LiFePO4 was probed in the in-situ Raman study. Under slow-rate discharge/charge, it was found that the particles were either fully transformed or untransformed indicating that the phase transition in LiFePO4 material was not uniform at the particle level. Electronic conductivity and local electrode microstructure determined the preferred sequence of phase transition of the particles. This study also revealed that non-equilibrium phase transition occurred as a result of delayed phase transition. The in-situ XRD study attempted to investigate the bulk level phase transition behavior of LiFePO4 and was conducted at four different discharge rates. Analysis of the high-resolution diffraction patterns showed a gradual and continuous change in phase transition. Again, a delayed phase transition was observed at high-rate discharge due to the non-equilibrium pathway. From both in-situ Raman and in-situ XRD experiments, only two stoichiometric compounds (LiFePO4 and FePO4) was detected, indicating that during electrochemical charge/discharge processes once Li ion de-intercalates/intercalates, it immediately forms the end-members and no intermediate compounds exist. Particle size and morphology of LiFePO4 were also studied using numerical models in the phase transition behavior. At a slow discharge rate, plate shaped particles showed higher capacity than spherical particles and the opposite trend was observed at high discharge rates above some critical discharge rates. Big particles and high discharge rates induced non-equilibrium phase transition in the LiFePO4 particles which expands the miscibility gap between the end-members and gave sharp narrow two-phase interfaces.

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

    PubMed

    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

  10. Water based processing of LiFePO4/C cathode material for Li-ion batteries utilizing freeze granulation

    NASA Astrophysics Data System (ADS)

    Orlenius, J.; Lyckfeldt, O.; Kasvayee, K. A.; Johander, P.

    2012-09-01

    A water based solid state synthesis of LiFePO4 has been conducted by utilizing freeze granulation. Various processing conditions were tested and achieved powder properties were characterized by density, XRD, specific surface area, carbon content, conductivity and SEM. Freeze granulation, a novel method for precursor preparation was shown to be an effective method to provide high degree of homogeneity prior to calcination and high ultimate yield of pure LiFePO4. Cathodes were manufactured by water based as well as NMP system based tape casting. A commercial LiFePO4/C powder was also characterized and used to manufacture cathodes as comparison in this study. Charge cycling tests showed promising results with high capacity and long term stability, well in the range of what the commercial powder provided. Post-milling of calcined powder prior to paste preparation for tape casting tended, however, to retard the capacity owing to disturbed carbon distribution and loss of conductivity of the LiFePO4/C. In comparison with the solvent system for cathode manufacturing, the water based system gave similar cell performance, illustrating the possibility to apply a more environmentally sustainable processing of Li-battery cells.

  11. Morphological characterization of LiFePO 4/C composite cathode materials synthesized via a carboxylic acid route

    NASA Astrophysics Data System (ADS)

    Fey, George Ting-Kuo; Lu, Tung-Lin

    A new type of LiFePO 4/C composite surrounded by a web containing both amorphous and crystalline carbon phases was synthesized by incorporating malonic acid as a carbon source using a high temperature solid-state method. SEM, TEM/SAED/EDS and HRTEM were used to analyze surface morphology and confirmed for the first time that crystalline carbon was present in LiFePO 4/C composites. The composite was effective in enhancing the electrochemical properties such as capacity and rate capability, because its active component consists of nanometer-sized particles containing pores with a wide range of sizes. An EDS elemental map showed that carbon was uniformly distributed on the surface of the composite crystalline particles. TEM/EDS results clearly show a dark region that is LiFePO 4 with a trace of carbon and a gray region that is carbon only. To evaluate the materials' electrochemical properties, galvanostatic cycling and conductivity measurements were performed. The best cell performance was delivered by the material coated with 60 wt.% malonic acid, which delivered first cycle discharge capacity of 149 mAh g -1 at a C/5 rate and sustained 222 cycles at 80% of capacity retention. When carboxylic acid was used as a carbon source to produce LiFePO 4, overall conductivity increased from 10 -5 to 10 -4 S cm -1, since particle growth was prevented during the final sintering process.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Crystal structure analysis and first principle investigation of F doping in LiFePO4

    NASA Astrophysics Data System (ADS)

    Milović, Miloš; Jugović, Dragana; Cvjetićanin, Nikola; Uskoković, Dragan; Milošević, Aleksandar S.; Popović, Zoran S.; Vukajlović, Filip R.

    2013-11-01

    This work presents the synthesis of F-doped LiFePO4/C composite by the specific modification of the recently suggested synthesis procedure based on an aqueous precipitation of precursor material in molten stearic acid, followed by a high temperature treatment. Besides the lattice parameters and the primitive cell volume reductions, compared to the undoped sample synthesized under the same conditions, the Rietveld refinement also shows that fluorine ions preferably occupy specific oxygen sites. Particularly, the best refinement is accomplished when fluorine ions occupy O(2) sites exclusively. By means of up-to-date electronic structure and total energy calculations this experimental finding is theoretically confirmed. Such fluorine doping also produces closing of the gap in the electronic structure and consequently better conductivity properties of the doped compound. In addition, the morphological and electrochemical performances of the synthesized powder are fully characterized.

  17. Electrochemical performance of LiFePO4 cylinder cell battery

    NASA Astrophysics Data System (ADS)

    Honggowiranto, Wagiyo; Sudaryanto, Kartini, Evvy; Purwanto, Agus

    2016-02-01

    A study on the electrochemical performance of LiFePO4 based cylinder cell battery has been done. The measurements have been carried out using cyclic voltametry (CV), charge-discharge (CD), and electrochemical impedance spectroscopy (EIS). The CV profiles showed that the battery exhibited anodic (charge) peak and chatodic (discharge) peak when scanned between 2.5 and 4.2V at various scan rate of 1 to 0.05 mV/s. The CD result showed that the battery capacity was 700 mAh exhibited excellent capacity retention with efficiency was about 100% after 100 cycles. From EIS measurement, it was also observed that the battery resistance decreased with the state of charge.

  18. Characterization of LiFePO4 cathode by addition of graphene for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Honggowiranto, Wagiyo; Kartini, Evvy

    2016-02-01

    The improvement of LiFePO4 (LFP) cathode performance has been performed by addition of Graphene (LFP+Graphene). The cathode was prepared from the active material with 5 wt % graphene and 10 wt % polyvinylidene fluoride in an n-methyl pyrrolidone solvent. Another cathode material used only 5% artificial graphite for comparison (LFP+Graphite). The crystal structure, microstructure, electronic conductivity, electrochemical impedance spectroscopy (EIS) of the cathodes were characterized by X-ray diffraction, SEM, and Impedance spectroscopy, respectively. Two half cell coin batteries were assembled using a lithium metal as an anode and LiPf6 as an electrolyte, and two cathodes (LFP+Graphene) and (LFP+Graphite). Charge discharge performance of battery was characterized by Battery analyser (BTS 8). The electronic conductivity of cathode with grapheme increased of about one order magnitude compared with the only cathode with graphite, namely from 1.97E-7S/cm (LFP+Graphite) to 1.92E-6S/cm (LFP+Graphene). The charge-discharge capacity after 10th cycles of LiFePO4 with graphene decreased of about 0.68% from 114.3 mAh/g to113.1 mAh/g, while LFP with graphite decreased of about 2.84% from 110.2 mAh/g to 107.1 mAh, at 0.1C-rates. It could be concluded that the addition of graphene has increased the ionic conductivity, and improved performance of the LFP lithium ion battery, such as higher capacity and better efficiency.

  19. Li-Ion Batteries from LiFePO4 Cathode and Anatase/Graphene Composite Anode for Stationary Energy Storage

    SciTech Connect

    Choi, Daiwon; Wang, Donghai; Viswanathan, Vilayanur V.; Bae, In-Tae; Wang, Wei; Nie, Zimin; Zhang, Jiguang; Graff, Gordon L.; Liu, Jun; Yang, Zhenguo; Duong, Tien Q.

    2009-11-06

    Li-ion batteries based on LiFePO4 cathode and anatase TiO2/graphene anode were investigated for possible stationary energy storage application. Fine-structured LiFePO4 was synthesized by novel molten surfactant approach. Anatase TiO2/graphene nanocomposite was prepared via self assembly method. The full cell that operated at flat 1.6V demonstrated negligible fade after more than 700 cycles. The LiFePO4/TiO2 combination Li-ion battery is inexpensive, environmentally benign, safe and stable. Therefore, it can be practically applied as stationary energy storage for renewable power sources.

  20. Electrochemical and XPS study of LiFePO4 cathode nanocomposite with PPy/PEG conductive network

    NASA Astrophysics Data System (ADS)

    Fedorková, A.; Oriňáková, R.; Oriňák, A.; Kupková, M.; Wiemhöfer, H.-D.; Audinot, J. N.; Guillot, J.

    2012-08-01

    High performance PPy/PEG-LiFePO4 nanocomposites as cathode materials were synthesized by solvothermal method and simple chemical oxidative polymerization of pyrrole (Py) monomer on the surface of LiFePO4 particles. The samples were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS) and charge-discharge tests. PPyPEG hybrid layers decrease particle to particle contact resistance while the impedance measurements confirmed that the coating of PPy-PEG significantly decreases the charge transfer resistance of the electrode material. The initial discharge capacities of this sample at C/5 and 1C are 150 and 128 mAh/g, respectively. The results show that PPy/PEGLiFePO4 composites are more effective than bare LiFePO4 as cathode material.

  1. 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.

  2. Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation.

    PubMed

    Liu, Xiaosong; Wang, Yung Jui; Barbiellini, Bernardo; Hafiz, Hasnain; Basak, Susmita; Liu, Jun; Richardson, Thomas; Shu, Guojiun; Chou, Fangcheng; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Moritz, Brian; Devereaux, Thomas P; Qiao, Ruimin; Chuang, Yi-De; Bansil, Arun; Hussain, Zahid; Yang, Wanli

    2015-10-21

    LiFePO4 is a battery cathode material with high safety standards due to its unique electronic structure. We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4 nanoparticles and single crystals. The results clearly show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. We focus on the energy configurations of the occupied states of LiFePO4 and the unoccupied states of FePO4, which are the critical states where electrons are removed and injected during the charge and discharge process, respectively. In LiFePO4, the soft X-ray emission spectroscopy shows that, due to the Coulomb repulsion effect, the occupied Fe-3d states with the minority spin sit close to the Fermi level. In FePO4, the soft X-ray absorption and hard X-ray Raman spectroscopy show that the unoccupied Fe-3d states again sit close to the Fermi level. These critical 3d electron state configurations are consistent with the calculations based on modified Becke and Johnson potentials GGA+U (MBJGGA+U) framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes. PMID:26388021

  3. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model

    NASA Astrophysics Data System (ADS)

    Delmas, C.; Maccario, M.; Croguennec, L.; Le Cras, F.; Weill, F.

    2008-08-01

    Lithium iron phosphate is one of the most promising positive-electrode materials for the next generation of lithium-ion batteries that will be used in electric and plug-in hybrid vehicles. Lithium deintercalation (intercalation) proceeds through a two-phase reaction between compositions very close to LiFePO4 and FePO4. As both endmember phases are very poor ionic and electronic conductors, it is difficult to understand the intercalation mechanism at the microscopic scale. Here, we report a characterization of electrochemically deintercalated nanomaterials by X-ray diffraction and electron microscopy that shows the coexistence of fully intercalated and fully deintercalated individual particles. This result indicates that the growth reaction is considerably faster than its nucleation. The reaction mechanism is described by a `domino-cascade model' and is explained by the existence of structural constraints occurring just at the reaction interface: the minimization of the elastic energy enhances the deintercalation (intercalation) process that occurs as a wave moving through the entire crystal. This model opens new perspectives in the search for new electrode materials even with poor ionic and electronic conductivities.

  4. 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

  5. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model.

    PubMed

    Delmas, C; Maccario, M; Croguennec, L; Le Cras, F; Weill, F

    2008-08-01

    Lithium iron phosphate is one of the most promising positive-electrode materials for the next generation of lithium-ion batteries that will be used in electric and plug-in hybrid vehicles. Lithium deintercalation (intercalation) proceeds through a two-phase reaction between compositions very close to LiFePO(4) and FePO(4). As both endmember phases are very poor ionic and electronic conductors, it is difficult to understand the intercalation mechanism at the microscopic scale. Here, we report a characterization of electrochemically deintercalated nanomaterials by X-ray diffraction and electron microscopy that shows the coexistence of fully intercalated and fully deintercalated individual particles. This result indicates that the growth reaction is considerably faster than its nucleation. The reaction mechanism is described by a 'domino-cascade model' and is explained by the existence of structural constraints occurring just at the reaction interface: the minimization of the elastic energy enhances the deintercalation (intercalation) process that occurs as a wave moving through the entire crystal. This model opens new perspectives in the search for new electrode materials even with poor ionic and electronic conductivities. PMID:18641656

  6. 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.

  7. 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.

  8. 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.

  9. Synthesis of cage-like LiFePO4/C microspheres for high performance lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Deng, Honggui; Jin, Shuangling; Zhan, Liang; Wang, Yanli; Qiao, Wenming; Ling, Licheng

    2012-12-01

    Cage-like LiFePO4 microspheres are synthesized by a solvothermal reaction-calcination process, using Fe(NO3)3·9H2O as iron source and ethylene glycol/water as co-solvent medium. The microsphere is the assembly of LiFePO4 nanoparticles with an open porous structure, thus the carbon coating can be easily introduced on the surface of the nanoparticles by the chemical vapor deposition of C2H4 during calcination process. When used as the cathode materials for the lithium-ion batteries, the resultant cage-like LiFePO4/C microsphere shows high capacity and good cycle stability (160 mAh g-1 at 0.1 C over 300 cycles), as well as good rate capability (120 mAh g-1 at 10 C). The desirable electrochemical performance can be attributed to high rate of ionic/electronic conduction and the high structural stability arising from the interconnected open pores, carbon-coated nanoparticles and microsized structure.

  10. 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. PMID:25846750

  11. 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.

  12. 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.

  13. 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.

  14. A facile route to modify ferrous phosphate and its use as an iron-containing resource for LiFePO4 via a polyol process.

    PubMed

    Li, Shaomin; Liu, Xichuan; Mi, Rui; Liu, Hao; Li, Yinchuan; Lau, Woon-min; Mei, Jun

    2014-06-25

    This study introduces an economical and environmentally friendly way of synthesizing LiFePO4/C to be used as cathode material in lithium ion batteries via two processes: (1) the synthesis of LiFePO4/C cathode material using a low cost divalent precursor ferrous phosphate, Fe3 (PO4)2·8H2O, as iron source in a polyol process and (2) the modification of the morphology of this precursor by varying the reaction time in a coprecipitation process. The study examines the effects of different structures and morphologies of the precursor on the structure and electrochemical performance of the as-synthesized LiFePO4/C. The LiFePO4/C shows an excellent rate capability and cycle performance, with initial discharge capacities of 153, 128, and 106 mA h g(-1) at 1 C, 5 C, and 10 C. The capacity retention is respectively 98.7%, 98.2%, and 98.7%, after 10 cycles at the corresponding rates. The capacity retention remains at 97% even after 300 cycles at the rate of 10 C. The outstanding electrochemical performance can be attributed to the improved rate of Li(+) diffusion and the excellent crystallinity of synthesized LiFePO4/C powders through the modified precursor. Therefore, this is an economical and environmentally friendly way of synthesizing LiFePO4/C to be used as cathode material in lithium ion batteries. PMID:24858212

  15. A simple and novel Si surface modification on LiFePO4@C electrode and its suppression of degradation of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Wenyu; Zhuang, Zhenyuan; Chen, Xiang; Zou, Mingzhong; Zhao, Guiying; Feng, Qian; Li, Jiaxin; Lin, Yingbin; Huang, Zhigao

    2015-12-01

    A simple and novel surface modification device of the electrodes based on the ultrasonic spray technique was set up, which is considered to have the enormous prospect of industrial application due to its simpleness and high efficiency. Then, the nano-sized Si nanoparticles were deposited uniformly on the LiFePO4@C electrodes. In comparison with pristine LiFePO4@C electrode, the surface modification of the nano-sized Si with crystalline Si core and amorphous Si shell on the electrode surface exhibits less coarsening degree, higher rate capability, better cyclicity at high charge/discharge rate, especially at elevated temperature. Moreover, Raman spectra of LiFePO4@C, LiFePO4@C/Si electrodes before cycles and after 100 cycles at 1 C and 60 °C were measured. It is found that the FePO4 and α-Fe2O3 phases exist in LiFePO4@C after 100 cycles. On the contrary, there hardly exists the FePO4 and α-Fe2O3 phases, which means that the nano Si surface modification suppresses the degradation of lithium ion batteries. At last, the schematic and phenomenological resistance models of LiFePO4@C electrode modified by the nano-sized silicon particles have been suggested, which is responsible for the enhancement of the electrochemical performances after nano-sized Si surface modification.

  16. 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). PMID:26305802

  17. 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. PMID:26934516

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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.

  19. 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

  20. 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. PMID:24526888

  1. Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes.

    PubMed

    Paolella, Andrea; Bertoni, Giovanni; Marras, Sergio; Dilena, Enrico; Colombo, Massimo; Prato, Mirko; Riedinger, Andreas; Povia, Mauro; Ansaldo, Alberto; Zaghib, Karim; Manna, Liberato; George, Chandramohan

    2014-12-10

    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

  2. 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.

  3. 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

  4. Electrochemical performance of NiO-doped LiFePO4/C cathode materials prepared from amorphous FePO4 · xH2O

    NASA Astrophysics Data System (ADS)

    Mahmud, Iqbal; Kim, Dong-Seob; Ur, Soon-Chul

    2016-05-01

    LiFePO4/C composites are prepared from amorphous FePO4 · xH2O and are modified with NiO (0.0, 0.01, 0.02, 0.03, and 0.04 mol) by using a solid-state reaction process with a spex milling system. The crystalline structure and the morphology of synthesized powders have been characterized by using X-ray diffraction (XRD) and scanning electron microscope (SEM). The XRD patterns indicate a complete solid solution for all the NiO-doped LiFePO4/C composites. The SEM images show that the sizes of the particles produced are distributed in the range of 200 - 300 nm. The electrochemical performances have been evaluated by using an impedance measurement and a galvanostatic charge/discharge test. The initial properties and impedance measurement reveal different improvements for different amounts of NiO doping in LiFePO4/C. A maximum capacity of 158.8 mAh/g at 0.1 C has been achieved LiFePO4/C doped with NiO at 0.01 mol. The present work reveals that the newly processed composite of LiFePO4/C doped with a small amount of NiO may be a promising material for using in a lithium-ion battery.

  5. 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.

  6. Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage.

    PubMed

    Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X S

    2015-05-21

    Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a "platelet-on-sheet" LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (∼56 mA h g(-1) at 60 C) and long life cycling stability (∼87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (∼98% capacity retention over 1000 cycles at 10 C). PMID:25908535

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

    PubMed

    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 Fe(3+) to Fe(2+) 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. Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method

    PubMed Central

    2012-01-01

    LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method. PMID:22221711

  9. 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.

  10. In situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates for superior Li-ion battery cathodes.

    PubMed

    Ma, Zhipeng; Fan, Yuqian; Shao, Guangjie; Wang, Guiling; Song, Jianjun; Liu, Tingting

    2015-02-01

    The low electronic conductivity and one-dimensional diffusion channel along the b axis for Li ions are two major obstacles to achieving high power density of LiFePO4 material. Coating carbon with excellent conductivity on the tailored LiFePO4 nanoparticles therefore plays an important role for efficient charge and mass transport within this material. We report here the in situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates with highly oriented (010) facets by introducing ferrocene as a catalyst during thermal treatment. The as-obtained material exhibits superior performances for Li-ion batteries at high rate (100 C) and low temperature (-20 °C), mainly because of fast electron transport through the graphitic carbon layer and efficient Li(+)-ion diffusion through the thin nanoplates. PMID:25584530

  11. Space matters: Li+ conduction versus strain effect at FePO4/LiFePO4 interface

    NASA Astrophysics Data System (ADS)

    Lv, Weiqiang; Niu, Yinghua; Jian, Xian; Zhang, Kelvin H. L.; Wang, Wei; Zhao, Jiyun; Wang, Zhiming; Yang, Weiqing; He, Weidong

    2016-02-01

    FePO4/LiFePO4 (FP/LFP) interfacial strain, giving rise to substantial variation in interfacial energy and lattice volume, is inevitable in the (de)lithiation process of LiFePO4, a prototype of Li ion battery cathodes. Extensive theoretical and experimental research has been focused on the effect of lattice strain energy on FP/LFP interface propagation orientation and cyclic stability of the electrode. However, the essential effect of strain induced lattice distortion on Li+ transport at the FP/LFP interface is typically overlooked. In this report, a coherent interface model is derived to evaluate quantitatively the correlation between FP/LFP lattice distortion and Li+ conduction. The results illustrate that the effect of lattice strain on Li+ conduction depends strongly on FP/LFP interface orientations. Lattice strain induces a 90% decrease of Li+ conductivity in ac-plane oriented (de)lithiation at room temperature. The opposite effect of lattice strain on delithiation and lithiation for ab- and bc-orientations is elucidated. In addition, the effect of lattice strain tends to be more pronounced at a lower working temperature. This study provides an efficient platform to comprehend and manipulate Li+ conduction in the charge and discharge of lithium ion batteries, the large-scale application of which is frequently challenged by limited in-cell ion conduction.

  12. Sequential Monte Carlo filter for state estimation of LiFePO4 batteries based on an online updated model

    NASA Astrophysics Data System (ADS)

    Li, Jiahao; Klee Barillas, Joaquin; Guenther, Clemens; Danzer, Michael A.

    2014-02-01

    Battery state monitoring is one of the key techniques in battery management systems e.g. in electric vehicles. An accurate estimation can help to improve the system performance and to prolong the battery remaining useful life. Main challenges for the state estimation for LiFePO4 batteries are the flat characteristic of open-circuit-voltage over battery state of charge (SOC) and the existence of hysteresis phenomena. Classical estimation approaches like Kalman filtering show limitations to handle nonlinear and non-Gaussian error distribution problems. In addition, uncertainties in the battery model parameters must be taken into account to describe the battery degradation. In this paper, a novel model-based method combining a Sequential Monte Carlo filter with adaptive control to determine the cell SOC and its electric impedance is presented. The applicability of this dual estimator is verified using measurement data acquired from a commercial LiFePO4 cell. Due to a better handling of the hysteresis problem, results show the benefits of the proposed method against the estimation with an Extended Kalman filter.

  13. 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.

  14. 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. PMID:26682389

  15. Enhancement of electrochemical behavior of nanostructured LiFePO4/Carbon cathode material with excess Li

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    We have synthesized carbon coated LiFePO4 (C-LiFePO4) and C-Li1.05FePO4 with 5 mol% excess Li via sol-gel method using oleic acid as a source of carbon for enhancing electronic conductivity and reducing the average particle size. Although the phase purity of the crystalline samples was confirmed by x-ray diffraction (XRD), the 57Fe Mössbauer spectroscopy analyses show the presence of ferric impurity phases in both stoichiometric and non-stoichiometric C-LiFePO4 samples. Transmission electron microscopy measurements show nanosized C-LiFePO4 particles uniformly covered with carbon, with average particle size reduced from ∼100 nm to ∼50 nm when excess lithium is used. Electrochemical measurements indicate a lower charge transfer resistance and better electrochemical performance for C-Li1.05FePO4 compared to that of C-LiFePO4. The aim of this work is to systematically analyze the nature of impurities formed during synthesis of LiFePO4 cathode material, and their impact on electrochemical performance. The correlation between the morphology, charge transfer resistance, diffusion coefficient and electrochemical performance of C-LiFePO4 and C- Li1.05FePO4 cathode materials are discussed.

  16. 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.

  17. 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

  18. Current density and state of charge inhomogeneities in Li-ion battery cells with LiFePO4 as cathode material due to temperature gradients

    NASA Astrophysics Data System (ADS)

    Fleckenstein, Matthias; Bohlen, Oliver; Roscher, Michael A.; Bäker, Bernard

    2011-05-01

    Current density distributions and local state of charge (SoC) differences that are caused by temperature gradients inside actively cooled Li-ion battery cells are discussed and quantified. As an example, a cylindrical Li-ion cell with LiFePO4 as cathode material (LiFePO4-cell) is analyzed in detail both experimentally and by means of spatial electro-thermal co-simulations. The reason for current density inhomogeneities is found to be the local electrochemical impedance varying with temperature in different regions of the jelly roll. For the investigated cell, high power cycling and the resulting temperature gradient additionally cause SoC-gradients inside the jelly roll. The local SoCs inside one cell diverge firstly because of asymmetric current density distributions during charge and discharge inside the cell and secondly because of the temperature dependence of the local open circuit potential. Even after long relaxation periods, the SoC distribution in cycled LiFePO4-cells remains inhomogeneous across the jelly roll as a result of hysteresis in the open circuit voltage. The occurring thermal electrical inhomogeneities are expected to influence local aging differences and thus, global cell aging. Additionally the occurrence of inhomogeneous current flow and SoC-development inside non-uniformly cooled battery packs of parallel connected LiFePO4-cells is measured and discussed.

  19. 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.

  20. Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation

    NASA Astrophysics Data System (ADS)

    Wang, Yung Jui; Liu, Xiaosong; Barbiellini, B.; Hafiz, Hasnain; Basak, Susmita; Liu, Jun; Richardson, Thomas; Shu, Guojiun; Chou, Fangcheng; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Moritz, B.; Devereaux, T. P.; Qiao, Ruimin; Chuang, Yi-De; Bansil, Arun; Hussain, Zahid; Yang, Wanli

    We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4. The results show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. The critical 3d electron state configurations are consistent with the calculations based on MBJGGA+U framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes. Work supported by the US DOE.

  1. Preparation and characterization of mesoporous LiFePO 4/C microsphere by spray drying assisted template method

    NASA Astrophysics Data System (ADS)

    Yu, Feng; Zhang, Jingjie; Yang, Yanfeng; Song, Guangzhi

    Mesoporous LiFePO 4/C microsphere was successfully prepared by spray drying assisted template method (SDATM) with citric acid as a template. This material has an average pore size of 50 nm and gives large specific surface area (32.2 m 2 g -1) with evenly distributed carbon (4.3 wt.%). It is also easy to bring into contact with electrolyte, facilitate the electric and lithium ion diffusion. It presents large reversible capacity of 158.8 mAh g -1 at C/10, even high rate capacity of 59.7 mAh g -1 at 20 C, and excellent capacity retention rate closed to 95.5% after various current densities.

  2. 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.

  3. Vacancy-driven anisotropic defect distribution in the battery-cathode material LiFePO4.

    PubMed

    Lee, Jaekwang; Zhou, Wu; Idrobo, Juan C; Pennycook, Stephen J; Pantelides, Sokrates T

    2011-08-19

    Li-ion mobility in LiFePO(4), a key property for energy applications, is impeded by Fe antisite defects (Fe(Li)) that form in select b-axis channels. Here we combine first-principles calculations, statistical mechanics, and scanning transmission electron microscopy to identify the origin of the effect: Li vacancies (V(Li)) are confined in one-dimensional b-axis channels, shuttling between neighboring Fe(Li). Segregation in select channels results in shorter Fe(Li)-Fe(Li) spans, whereby the energy is lowered by the V(Li)'s spending more time bound to end-point Fe(Li)'s. V(Li)-Fe(Li)-V(Li) complexes also form, accounting for observed electron energy loss spectroscopy features. PMID:21929178

  4. Simplified electrochemical multi-particle model for LiFePO4 cathodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mastali Majdabadi, Mehrdad; Farhad, Siamak; Farkhondeh, Mohammad; Fraser, Roydon A.; Fowler, Michael

    2015-02-01

    A simplified physics-based model is developed to predict the performance of an LiFePO4 cathode at various operating and design conditions. Newman's full-order porous-electrode model is simplified using polynomial approximations for electrolyte variables at the electrode-level while a multi-particle model featuring variable solid-state diffusivity is employed at the particle level. The computational time of this reduced-order model is decreased by almost one order of magnitude compared to the full-order model without sacrificing the accuracy of the results. The model is general and can be used to expedite the simulation of any composite electrode with active-material particles of non-uniform properties (e.g., size, contact resistance, material chemistry etc.). In a broader perspective, this model is of practical value for electric vehicle power train simulations and battery management systems.

  5. Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X. S.

    2015-05-01

    Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a ``platelet-on-sheet'' LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (~56 mA h g-1 at 60 C) and long life cycling stability (~87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (~98% capacity retention over 1000 cycles at 10 C).Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a ``platelet-on-sheet'' LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (~56 mA h g-1 at 60 C) and long life cycling stability (~87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (~98% capacity retention over 1000 cycles at 10 C). Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01831e

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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

  11. 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

  12. LiFePO 4: From molten ingot to nanoparticles with high-rate performance in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Charest, P.; Dontigny, M.; Guerfi, A.; Lagacé, M.; Mauger, A.; Kopec, M.; Julien, C. M.

    LiFePO 4 (LFP) particles were obtained by grinding ingot synthesized in the molten state. This process, followed by jet milling, and then wet milling, provides a simple way to obtain powders with controlled particle size in the range from macroscopic to 25 nm. However, at this time, we find that these particles tend to agglomerate to form secondary particles of size ∼100 nm. The particles obtained by this process are characterized by X-ray diffraction (XRD). In situ and ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effect of milling was also investigated by analysis of physical properties using infrared spectroscopy (FTIR) and magnetic measurements. The electrochemical performance was evaluated in cells containing Li/1 M LiPF 6 in EC:DEC (1:1)/C-LiFePO 4. After carbon coating, the LFP particles which are free of impurities, exhibit high-rate capability. Even with a limited amount of carbon (2 wt.%) appropriate for commercial batteries, the capacity is 157 mAh g -1 at 0.1 C, 120 mAh g -1 at 10 C, without capacity fading after 60 cycles.

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

    PubMed

    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. State-of-health estimation of LiFePO4/graphite batteries based on a model using differential capacity

    NASA Astrophysics Data System (ADS)

    Torai, Soichiro; Nakagomi, Masaru; Yoshitake, Satoshi; Yamaguchi, Shuichiro; Oyama, Noboru

    2016-02-01

    A model for expressing the differential capacity characteristics of the LiFePO4 (LFP)/graphite battery for the state-of-health (SOH) estimation was proposed. Our model was based on the deformed pseudo-Voigt peak function with several parameters which are directly associated with the phase transition behavior of the active LFP and graphite materials. Charge/discharge cycle tests for accelerated battery fading were performed under a constant high-temperature condition (40 and 45 °C). The SOH estimation was carried out at different fading point of the battery using a part of the responses for the differential capacity versus voltage (dQ/dV vs. V) against the charging process at the rate of C/5 under constant temperature of 25 °C. The changes in the variables of the model with cycling were correlated to the generally mentioned phenomena that the main factors determining the capacity fading of the LFP/graphite battery are the loss of Li+ by a side reaction and that of the active electrode materials. In addition, the robustness related to the charge/discharge history was confirmed, since the memory effect of the LFP/graphite battery, being induced by the previous condition for use, has an influence on the dQ/dV vs. V. The evaluated SOH errors were within ±3%.

  15. Electron microscopy investigations of changes in morphology and conductivity of LiFePO4/C electrodes

    NASA Astrophysics Data System (ADS)

    Scipioni, Roberto; Jørgensen, Peter S.; Ngo, Duc-The; Simonsen, Søren B.; Liu, Zhao; Yakal-Kremski, Kyle J.; Wang, Hongqian; Hjelm, Johan; Norby, Poul; Barnett, Scott A.; Jensen, Søren H.

    2016-03-01

    In this work we study the structural degradation of a laboratory Li-ion battery LiFePO4/Carbon Black (LFP/CB) cathode by various electron microscopy techniques including low kV Focused Ion Beam (FIB)/Scanning Electron Microscopy (SEM) 3D tomography. Several changes are observed in FIB/SEM images of fresh and degraded cathodes, including cracks in the LFP particles, secondary disconnected particles, and agglomeration of CB. Low voltage (1 kV) SEM images show that the CB agglomerates have a different brightness than the fresh CB, due to charging effects. This suggests that the electronic conductivity of the CB agglomerates is low compared to that of the fresh CB particles. HRTEM analysis shows that fresh CB particles are quasi crystalline, whereas the LFP/CB interface in the degraded electrode shows amorphous carbon surrounding the LFP particles. The presence of the amorphous carbon is known to impede the electronic conductivity and thereby decreasing percolation in the cathode and reducing the electrode capacity.

  16. 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.

  17. 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

  18. 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

    2015-01-01

    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

  19. 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.

  20. 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.

  1. 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

  2. Increasing the Affinity Between Carbon-Coated LiFePO4/C Electrodes and Conventional Organic Electrolyte by Spontaneous Grafting of a Benzene-Trifluoromethylsulfonimide Moiety.

    PubMed

    Delaporte, Nicolas; Perea, Alexis; Lebègue, Estelle; Ladouceur, Sébastien; Zaghib, Karim; Bélanger, Daniel

    2015-08-26

    The grafting of benzene-trifluoromethylsulfonimide groups on LiFePO4/C was achieved by spontaneous reduction of in situ generated diazonium ions of the corresponding 4-amino-benzene-trifluoromethylsulfonimide. The diazotization of 4-amino-benzene-trifluoromethylsulfonimide was a slow process that required a high concentration of precursors to promote the spontaneous grafting reaction. Contact angle measurements showed a hydrophilic surface was produced after the reaction that is consistent with grafting of benzene-trifluoromethylsulfonimide groups. Elemental analysis data revealed a 2.1 wt % loading of grafted molecules on the LiFePO4/C powder. Chemical oxidation of the cathode material during the grafting reaction was detected by X-ray diffraction and quantified by inductively coupled plasma atomic emission spectrometry. Surface modification improves the wettability of the cathode material, and better discharge capacities were obtained for modified electrodes at high C-rate. In addition, electrochemical impedance spectroscopy showed the resistance of the modified cathode was lower than that of the bare LiFePO4/C film electrode. Moreover, the modified cathode displayed superior capacity retention after 200 cycles of charge/discharge at 1 C. PMID:26186016

  3. Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

    PubMed

    Kadyk, Thomas; Eikerling, Michael

    2015-08-14

    The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs. PMID:26156571

  4. 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. PMID:25430976

  5. 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.

  6. Particle shapes and surface structures of olivine NaFePO₄ in comparison to LiFePO₄.

    PubMed

    Whiteside, Alexander; Fisher, Craig A J; Parker, Stephen C; Islam, M Saiful

    2014-10-21

    The expansion of batteries into electric vehicle and grid storage applications has driven the development of new battery materials and chemistries, such as olivine phosphate cathodes and sodium-ion batteries. Here we present atomistic simulations of the surfaces of olivine-structured NaFePO4 as a sodium-ion battery cathode, and discuss differences in its morphology compared to the lithium analogue LiFePO4. The calculated equilibrium morphology is mostly isometric in appearance, with (010), (201) and (011) faces dominant. Exposure of the (010) surface is vital because it is normal to the one-dimensional ion-conduction pathway. Platelet and cube-like shapes observed by previous microscopy studies are reproduced by adjusting surface energies. The results indicate that a variety of (nano)particle morphologies can be achieved by tuning surface stabilities, which depend on synthesis methods and solvent conditions, and will be important in optimising electrochemical performance. PMID:25200320

  7. Synthesis and performances of 2LiFePO4·Li3V2(PO4)3/C cathode materials via spray drying method with double carbon sources

    NASA Astrophysics Data System (ADS)

    Zhang, Jia-feng; Shen, Chao; Zhang, Bao; Zheng, Jun-chao; Peng, Chun-li; Wang, Xiao-wei; Yuan, Xin-bo; Li, Hui; Chen, Guo-min

    2014-12-01

    The 2LiFePO4·Li3V2(PO4)3/C samples are synthesized through spray drying method. Glucose and oxalic acid are used as collaborative carbon sources to improve the electrochemical performance of 2LiFePO4·Li3V2(PO4)3/C composites. XRD results reveal the LiFePO4·Li3V2(PO4)3/C samples are composed of orthorhombic LiFePO4 and monoclinic Li3V2(PO4)3 phases. SEM results reveal that the nano-spherical Fe4(VO4)4·5H2O are about 80 nm and the 2LiFePO4·Li3V2(PO4)3/C composites possess a micro-nano spherical morphology with carbon coating layer. The samples show the best electrochemical performance when the mass ration of glucose and oxalic is 6:4, it can deliver a capacity of 147.6 mAh g-1, 145.0 mAh g-1, 134.1 mAh g-1 and 123.0 mAh g-1 at the rates of 0.1C, 1C, 5C and 10C, respectively.

  8. 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.

  9. 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

  10. 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.

  11. Irreversible phase transition between LiFePO4 and FePO4 during high-rate charge-discharge reaction by operando X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Takahashi, Ikuma; Mori, Takuya; Yoshinari, Takahiro; Orikasa, Yuki; Koyama, Yukinori; Murayama, Haruno; Fukuda, Katsutoshi; Hatano, Masaharu; Arai, Hajime; Uchimoto, Yoshiharu; Terai, Takayuki

    2016-03-01

    LiFePO4 is a practically used cathode material for lithium-ion batteries due to a high theoretical capacity, high cycle capability and the high-rate performance. The metastable LixFePO4 (LxFP) phase with an intermediate composition appears in the non-equilibrium state at high-rate condition. However, the formation process of the metastable LxFP phase and its impact to the electrochemical property are still unclear. In order to elucidate these points, we directly observed the phase transition behavior by applying operando XRD during 10C charge-discharge. LxFP phase does not form in charge reaction but preferentially forms in discharge reaction. The phase transition from LxFP to Li-rich phase is less likely to proceed in the end of discharge reaction. The asymmetric phase transition between LiFePO4 and FePO4 results in decreasing the discharge capacity and increasing the irreversible capacity at high-rate conditions.

  12. Length-Scale-Dependent Phase Transformation of LiFePO4 : An In situ and Operando Study Using Micro-Raman Spectroscopy and XRD.

    PubMed

    Siddique, N A; Salehi, Amir; Wei, Zi; Liu, Dong; Sajjad, Syed D; Liu, Fuqiang

    2015-08-01

    The charge and discharge of lithium ion batteries are often accompanied by electrochemically driven phase-transformation processes. In this work, two in situ and operando methods, that is, micro-Raman spectroscopy and X-ray diffraction (XRD), have been combined to study the phase-transformation process in LiFePO4 at two distinct length scales, namely, particle-level scale (∼1 μm) and macroscopic scale (∼several cm). In situ Raman studies revealed a discrete mode of phase transformation at the particle level. Besides, the preferred electrochemical transport network, particularly the carbon content, was found to govern the sequence of phase transformation among particles. In contrast, at the macroscopic level, studies conducted at four different discharge rates showed a continuous but delayed phase transformation. These findings uncovered the intricate phase transformation in LiFePO4 and potentially offer valuable insights into optimizing the length-scale-dependent properties of battery materials. PMID:26073651

  13. Percolation-tunneling modeling for the study of the electric conductivity in LiFePO 4 based Li-ion battery cathodes

    NASA Astrophysics Data System (ADS)

    Awarke, Ali; Lauer, Sven; Pischinger, Stefan; Wittler, Michael

    In this work a percolation-tunneling based model is developed and used to study the electrical conductivity of LiFePO 4 composite Li-ion battery cathodes. The active and conductive additive particles are explicitly represented using a random hybrid geometric-mechanical packing algorithm, while the inter-particle electric transport is achieved by including electron tunneling effects. The model is adjusted to the experimental data of a PVDF/C composite with different mixing ratios. The performed study aims to capture the variation of the conductivity of the LiFePO 4 cathode with particle sizes, carbon black particles wt.% and carbon coating wt.%. It is found that ultra fine carbon-free nanosized particles (∼50 nm), which are favorable for improved diffusion, would require a relatively high amount of carbon black (15 wt.%) putting at risk the gravimetric capacity of the cell. On the other hand, particles with 1 wt.% continuous carbon coating delivers already sufficient conductivity for all particle sizes without any additives. The further addition of conductive phases is at the risk of redundancy in view of conductivity enhancements. Although continuous carbon coating with loading as low as 1 wt.% is thought to be the most efficient way to achieve electric conductivity, its manufacturability and effect on Li ion diffusion remain to be assessed.

  14. Phase evolution in single-crystalline LiFePO4 followed by in situ scanning X-ray microscopy of a micrometre-sized battery

    NASA Astrophysics Data System (ADS)

    Ohmer, Nils; Fenk, Bernhard; Samuelis, Dominik; Chen, Chia-Chin; Maier, Joachim; Weigand, Markus; Goering, Eberhard; Schütz, Gisela

    2015-01-01

    LiFePO4 is one of the most frequently studied positive electrode materials for lithium-ion batteries during the last years. Nevertheless, there is still an extensive debate on the mechanism of phase transformation. On the one hand this is due to the small energetic differences involved and hence the great sensitivity with respect to parameters such as size and morphology. On the other hand this is due to the lack of in situ observations with appreciable space and time resolution. Here we present scanning transmission X-ray microscopy measurements following in situ the phase boundary propagation within a LiFePO4 single crystal along the (010) orientation during electrochemical lithiation/delithiation. We follow, on a battery-relevant timescale, the evolution of a two-phase-front on a micrometre scale with a lateral resolution of 30 nm and with minutes of time resolution. The growth pattern is found to be dominated by elastic effects rather than being transport-controlled.

  15. Insights in the electronic structure and redox reaction energy in LiFePO4 battery material from an accurate Tran-Blaha modified Becke Johnson potential

    NASA Astrophysics Data System (ADS)

    B. Araujo, Rafael; S. de Almeida, J.; Ferreira da Silva, A.; Ahuja, Rajeev

    2015-09-01

    The main goals of this paper are to investigate the accuracy of the Tran-Blaha modified Becke Johnson (TB-mBJ) potential to predict the electronic structure of lithium iron phosphate and the related redox reaction energy with the lithium deintercalation process. The computed electronic structures show that the TB-mBJ method is able to partially localize Fe-3d electrons in LiFePO4 and FePO4 which usually is a problem for the generalized gradient approximation (GGA) due to the self interaction error. The energy band gap is also improved by the TB-mBJ calculations in comparison with the GGA results. It turned out, however, that the redox reaction energy evaluated by the TB-mBJ technique is not in good agreement with the measured one. It is speculated that this disagreement in the computed redox energy and the experimental value is due to the lack of a formal expression to evaluate the exchange and correlation energy. Therefore, the TB-mBJ is an efficient method to improve the prediction of the electronic structures coming form the standard GGA functional in LiFePO4 and FePO4. However, it does not appear to have the same efficiency for evaluating the redox reaction energies for the investigated system.

  16. 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.

  17. 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.

  18. 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).

  19. Enhanced electrochemical properties of LiFePO4 (LFP) cathode using the carboxymethyl cellulose lithium (CMC-Li) as novel binder in lithium-ion battery.

    PubMed

    Qiu, Lei; Shao, Ziqiang; Wang, Daxiong; Wang, Wenjun; Wang, Feijun; Wang, Jianquan

    2014-10-13

    Novel water-based binder CMC-Li is synthesized using cotton as raw material. The mechanism of the CMC-Li as a binder is reported. Electrochemical properties of batteries cathodes based on commercially available lithium iron phosphate (LiFePO4, LFP) and CMC-Li as a water-soluble binder are investigated. CMC-Li is a novel lithium-ion binder. Compare with conventional poly(vinylidene fluoride) (PVDF) binder, and the battery with CMC-Li as the binder retained 97.8% of initial reversible capacity after 200 cycles at 176 mAh g(-1), which is beyond the theoretical specific capacity of LFP. Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, follow closely by that using PVDF binder. The batteries have good electrochemical property, outstanding pollution-free and excellent stability. PMID:25037391

  20. 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.

  1. 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

  2. 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.

  3. Artificial meteor ablation studies: Olivine

    NASA Technical Reports Server (NTRS)

    Blanchard, M. B.; Cunningham, G. G.

    1973-01-01

    Artificial meteor ablation was performed on a Mg-rich olivine sample using an arc-heated plasma of ionized air. Experimental conditions simulated a meteor traveling about 12 km/sec at an altitude of 70 km. The mineral content of the original olivine sample was 98% olivine (including traces of olivine alteration products) and 2% chromite. Forsterite content of the original olivine was Fo-89. After ablation, the forsterite content had increased to Fo-94 in the recrystallized olivine. In addition, lamella-like intergrowths of magnetite were prevalent constituents. Wherever magnetite occurred, there was an increase in Mg and a corresponding decrease in Fe for the recrystallized olivine. The Allende fusion crust consisted of a recrystallized olivine, which was more Mg-rich and Fe-deficient than the original meteorite's olivine, and abundant magnetite grains. Although troilite and pentlandite were the common opaque mineral constituents in this meteorite, magnetite was the principal opaque mineral found in the fusion crust.

  4. 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.

  5. 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. PMID:25565086

  6. Vacuum welding of olivine.

    PubMed

    Bell, P R

    1966-07-22

    Welding of olivine was demonstrated by grinding it in a ball mill in an atmosphere of about 2 x 10(-7) torr. Most of the sample adhered strongly to the container and grinding balls although adhesion in air is only slight. Similar adhesion should be expected on the lunar surface and may account for the roughness needed to explain the optical properties of the moon and the detail of the una 9 photographs. PMID:17839712

  7. "Black-colored olivines" in peridotites: dehydrogenation from hydrous olivines

    NASA Astrophysics Data System (ADS)

    Arai, Shoji; Hoshikawa, Chihiro; Miura, Makoto

    2015-04-01

    Fresh olivines that are black to the naked eye are found in some dunites. Peridotites are easily converted to be black in color, when serpentinized, due to production of secondary fine magnetite particles. The dunites that contain fresh but black-colored olivines are usually coarse-grained. These coarse olivine grains are sometimes very heterogeneous in color; the blackish part grades to whitish parts in single grains. The black color is due to homegeneous distribution of minute (< 10 microns) black particles in olivine. They are rod-like or plate-like in shape in thin section, sometimes being aligned under crystallographic control of the host olivine. Olivines are clear and free of these inclusions around primary chromian spinel inclusions or chromian spinel lamellae (Arai, 1978). Raman spectroscopy indicates the minute black particles are magnetite always associated with diopside. It is interesting to note that olivine in mantle peridotites accompanied by the black-colored dunites is totally free of the black inclusions, giving the ordinary colors (pale yellow to whitish) of Mg-rich olivine. It is not likely that the magnetite inclusions formed through secondary oxidation of olivine by invasion of oxygen, which is possible along cracks or grain boundaries. They most probably formed due to dehydrogenation from primary OH-bearing olivines upon cooling. Hydrogen was quickly diffused out from the olivines to leave magnetite and excess silica. The excess silica was possibly combined with a monticellite component to form diopside. The OH-bearing (hydrous) olivines can be precipitated from hydrous magmas, and the hydrous nature of the magma can promote an increase in grain size due to faster diffusion of elements. The minute inclusions of magnetite + diopside is thus an indicator of primary hydrous character of host olivine.

  8. 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.

  9. Conformal Coating Strategy Comprising N-doped Carbon and Conventional Graphene for Achieving Ultrahigh Power and Cyclability of LiFePO4.

    PubMed

    Zhang, Kan; Lee, Jeong-Taik; Li, Ping; Kang, Byoungwoo; Kim, Jung Hyun; Yi, Gi-Ra; Park, Jong Hyeok

    2015-10-14

    Surface carbon coating to improve the inherent poor electrical conductivity of lithium iron phosphate (LiFePO4, LFP) has been considered as most efficient strategy. Here, we also report one of the conventional methods for LFP but exhibiting a specific capacity beyond the theoretical value, ultrahigh rate performance, and excellent long-term cyclability: the specific capacity is 171.9 mAh/g (70 μm-thick electrode with ∼10 mg/cm(2) loading mass) at 0.1 C (17 mA/g) and retains 143.7 mAh/g at 10 C (1.7 A/g) and 95.8% of initial capacity at 10 C after 1000 cycles. It was found that the interior conformal N-C coating enhances the intrinsic conductivity of LFP nanorods (LFP NR) and the exterior reduced graphene oxide coating acts as an electrically conducting secondary network to electrically connect the entire electrode. The great electron transport mutually promoted with shorten Li diffusion length on (010) facet exposed LFP NR represents the highest specific capacity value recorded to date at 10 C and ultralong-term cyclability. This conformal carbon coating approach can be a promising strategy for the commercialization of LFP cathode in lithium ion batteries. PMID:26389552

  10. 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.

  11. 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.

  12. 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.

  13. Experiment and simulation of a LiFePO4 battery pack with a passive thermal management system using composite phase change material and graphite sheets

    NASA Astrophysics Data System (ADS)

    Lin, Chunjing; Xu, Sichuan; Chang, Guofeng; Liu, Jinling

    2015-02-01

    A passive thermal management system (TMS) for LiFePO4 battery modules using phase change material (PCM) as the heat dissipation source to control battery temperature rise is developed. Expanded graphite matrix and graphite sheets are applied to compensate low thermal conductivity of PCM and improve temperature uniformity of the batteries. Constant current discharge and mixed charge-discharge duties were applied on battery modules with and without PCM on a battery thermal characteristics test platform. Experimental results show that PCM cooling significantly reduces the battery temperature rise during short-time intense use. It is also found that temperature uniformity across the module deteriorates with the increasing of both discharge time and current rates. The maximum temperature differences at the end of 1C and 2C-rate discharges are both less than 5 °C, indicating a good performance in battery thermal uniformity of the passive TMS. Experiments on warm-keeping performance show that the passive TMS can effectively keep the battery within its optimum operating temperature for a long time during cold weather uses. A three dimensional numerical model of the battery pack with the passive TMS was conducted using ANSYS Fluent. Temperature profiles with respect to discharging time reveal that simulation shows good agreement with experiment at 1C-discharge rate.

  14. 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.

  15. Minor elements in Marjalahti olivine

    NASA Astrophysics Data System (ADS)

    Ryder, G.

    1984-06-01

    Precise microprobe determinations of minor elements in olivine from Marjalahti show averages of 0.0267 percent CaO; 0.0211 percent Cr2O3; less than 0.0045 percent TiO2; 0.288 percent MnO; and 30 ppm Ni. The calcium is as high as in some terrestrial plutonic olivines (e.g. Stillwater) but lower than in terrestrial nodule (high-temperature mantle?) olivines, consistent with very slow cooling to low temperatures. The chromium is discrepant with some earlier determinations, and possibly chromium is zoned in most pallasitic olivines. The Ti, Mn, and Ni data are consistent with previous determinations.

  16. Olivine flotation in mantle melt

    NASA Astrophysics Data System (ADS)

    Agee, Carl B.; Walker, David

    1993-01-01

    Molten komatiite and peridotite have been compressed in an octahedral multi-anvil device up to 10 GPa. Densities of the melts were measured at pressure intervals in the range 7 to 10 GPa by observing sinking and floating San Carlos olivines and synthetic forsterite marker spheres. The multi-anvil results for komatiite, when combined with piston-cylinder measurements done at 4 to 6 GPa and a calculated reference density at 10 5 Pa, yield a Birch-Murnaghan isothermal bulk modulus of (K 1900C) = 26 GPa and pressure derivative K' = 4.25. The pressure of neutral buoyancy for olivine in komatiite is confirmed to be near 8 GPa as predicted in earlier work. Olivine flotation in the experimental komatiite commences at a pressure close to where the liquidus phase changes from olivine to denser garnet, leading to the possibility of density driven crystal sorting during fractionation. Molten peridotite (KLB-1) shows an isothermal compression (2000°C) of 0.065 g cm -3 GPa -1 in the interval 10 5 Pa to 8.2 GPa. The olivine/liquid peridotite density crossover is predicted to lie between 9 and 11 GPa, indicating that olivine flotation can operate at depths of 300-500 km in a molten peridotitic mantle.

  17. 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

  18. Porous micro-spherical aggregates of LiFePO 4/C nanocomposites: A novel and simple template-free concept and synthesis via sol-gel-spray drying method

    NASA Astrophysics Data System (ADS)

    Yu, Feng; Zhang, Jingjie; Yang, Yanfeng; Song, Guangzhi

    Porous micro-spherical aggregates of LiFePO 4/C nanocomposites were prepared with a process of spray drying at 200 °C and subsequent heat treatment at 700 °C for 12 h by a novel and simple template-free sol-gel-SD method independent of surfactants or templates. The results indicate that the as-obtained LiFePO 4 porous microspheres have the mean diameter of 19.8 μm, average pore size of 45 nm, and large specific surface area (20.2 m 2 g -1) with evenly distributed carbon (4.5 wt.%). The particles can be easily brought into contact with electrolyte, facilitating electric and lithium ion diffusion. They present large reversible discharge capacity of 137.5 mAh g -1 at the current density of 0.1 C, good rate capacity of 53.8 mAh g -1 at 10 C, and excellent capacity retention rate closed to 100% after various current densities in the region of 2.0-4.3 V.

  19. 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.

  20. Studies on graphene enfolded olivine composite electrode material via polyol technique for high rate performance lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Muruganantham, Rasu; Sivakumar, Marimuthu; Subadevi, Rengapillai; Ramaprabhu, Sundara; Wu, Nae-Lih

    2015-09-01

    The graphene enfolded LiFePO4/C composite cathode material has been prepared via low temperature polyol process, followed by a simple chemical reaction method. The low viscous polyol solvent (DEG) (35.7 mPa s at 25°C) and usage of low temperature process (below 245°C) aid the graphene tightly encapsulated on the LiFePO4 surface that plays an important role, especially in the high rate performances over long cycles, efficiently preventing the separation of the graphene and LiFePO4 during the reaction processes, hence realizing the full potential of the active materials. The graphitization on LiFePO4/C remarkably increased the electronic conductivity of LiFePO4. The layered sheets of graphene wrapped on LiFePO4 particles provide void between graphene sheets and LiFePO4 surfaces, which facilitate the diffusion of Li+. This approach opens up a method to attain the theoretical capacity of LiFePO4. The material exhibits a superior electrochemical performance such as initial discharge capacities of 169.6 and 92 mAhg-1 at 0.1 and 30 C rates, respectively. It has an excellent capacity retention and diminutive capacity fading. The nanosize of LiFePO4 particle causes a shorter diffusion path, which reduces the time for Li+ migration between cathode and electrolyte. [Figure not available: see fulltext.

  1. 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.

  2. 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.

  3. More on the performance of LiFePO 4 electrodes-The effect of synthesis route, solution composition, aging, and temperature

    NASA Astrophysics Data System (ADS)

    Koltypin, M.; Aurbach, D.; Nazar, L.; Ellis, B.

    Three types of olivine compounds were prepared by three different routes: sol-gel, solid-state, and hydrothermal syntheses, showing the expected structure and containing a small amount of carbon and iron phosphide for maintaining sufficient intrinsic electrical conductivity. These materials were tested in LiClO 4, and in dry and wet LiPF 6 solutions in mixtures of ethylene and dimethyl carbonate (EC-DMC, 1:1) at 30 and 60 °C. Iron dissolution from these materials, upon storage in the three solutions at these two temperatures, was measured by ICP. Aged electrodes were measured by XRD and SEM: the electrochemical performance of the three types of olivine compounds in the three solutions and at the two temperatures was measured by voltammetry and impedance spectroscopy. The behavior of pristine and aged electrodes was systematically compared. It was found that there is a strong correlation between the rate of iron dissolution and the performance of these systems in terms of high capacity, low capacity fading, and low and stable impedance upon aging. The material prepared by sol-gel synthesis demonstrated a low iron dissolution rate, even in a corrosive solution such as wet LiPF 6 solutions, and high performance, even in these solutions. When the solutions contain no acidic contaminants, all the compounds demonstrated negligible iron dissolution rates, even at 60 °C, and a good electrochemical performance. The electrochemical comparison described herein shows a pronounced impact of the solution composition on the electrodes' impedance, due to the unique surface chemistry developed in each solution.

  4. 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. PMID:26207862

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. A reduced order electrochemical and thermal model for a pouch type lithium ion polymer battery with LiNixMnyCo1-x-yO2/LiFePO4 blended cathode

    NASA Astrophysics Data System (ADS)

    Li, Xueyan; Choe, Song-Yul; Joe, Won Tae

    2015-10-01

    LiNixMnyCo1-x-yO2 (NMC) and LiFePO4 (LFP) as a cathode material have been widely employed for cells designed for high power applications. However, NMC needs further improvements in rate capability and stability that can be accomplished by blending it with LFP. Working mechanism of the blended cells is very complex and hard to understand. In addition, characteristics of the blended cells, particularly the plateau and path dependence of LFP materials, make it extremely difficult to estimate the state of charge and state of health using classical electric equivalent circuit models. Therefore, a reduced order model based on electrochemical and thermal principles is developed with objectives for real time applications and validated against experimental data collected from a large format pouch type of lithium ion polymer battery. The model for LFP is based on a shrinking core model along with moving boundary and then integrated into NMC model. Responses of the model that include SOC estimation and responses of current and voltage are compared with those of experiments at CC/CV charging and CC discharging along with different current rates and temperatures. In addition, the model is used to analyze effects of mass ratios between two materials on terminal voltage and heat generation rate.

  10. 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

  11. 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.

    2016-04-01

    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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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. PMID:25970716

  17. Investigation of sodium insertion-extraction in olivine NaxFePO4 (0 ≤x≤ 1) using first-principles calculations.

    PubMed

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

    2016-05-14

    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 Fe(2+)/Fe(3+) 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. PMID:27110665

  18. 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.

  19. 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.

  20. Aligned Olivine in the Springwater Pallasite

    NASA Astrophysics Data System (ADS)

    Fowler-Gerace, N.; Tait, K.; Moser, D.; Barker, I.; Tian, B. Y.

    2014-12-01

    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. Klosterman and Buseck [1] found no crystallographic preferred orientation of olivine in nine pallasites, but the Leitz five-axis universal stage method imposed limitations on precision (estimated within ˜4◦) and sample size (only 10 crystals were measured in the Springwater pallasite, for instance). Using Electron Backscatter Diffraction, we have collected crystallographic orientation data (accurate to ±0.5◦ [2]) for 343 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 our thorough characterization of large-scale Springwater textures, the definitively non-random spatial distribution of olivine orientations reveals the nature of the olivine's initial formation environment as well as the sequence of events subsequent to metal incorporation. [1] Klosterman and Buseck. 1973. J Geophys Res 78(32):7581-7588. [2] Oxford Instruments. 2013. http://www.ebsd.com/.

  1. Incompatible Trace Element Abundances in Hawaiian Olivines

    NASA Astrophysics Data System (ADS)

    Yu, G.; Huang, S.; Mukhopadhyay, S.; Jacobsen, S. B.

    2009-12-01

    Our understanding of trace elements partitioning between olivine and silicate melt is clouded by large variations in values of partition coefficients presented in the literature. In general, partition coefficients from phenocryst-matrix results are higher than those from experimental equilibration and in-situ measurements (such as LA-ICP-MS and Ion-probe) (Blard and Farley, 2008; Lee et al., 2007). This discrepancy is possibly caused by the presence of melt or micromineral inclusions in the analyzed phenocrysts, or contamination of grain boundaries by enriched glasses or accessory phases or uranium pick up from alteration of olivines. To further investigate why analysis of natural phenocrysts usually results in relative high apparent D’s for incompatible trace elements, six aliquots of olivine grains from a single sediment sample of Waimea river watershed, on the western side of the island of Kauai, Hawaii, were analyzed by solution ICP-MS at Harvard University for trace element concentrations. Two aliquots of olivines were leached in 1% oxalic acid for 45-60 min at 90 OC before dissolution. Leached and unleached olivines mostly show positive linear correlations in plots of incompatible trace elements versus La, which possibly indicates mixing lines between olivine and one end-member with higher incompatible element concentration (possibly melt inclusion). Assuming La concentration in olivine is zero, we estimate concentration of other incompatible elements in olivines using intercepts of these mixing lines. We obtain that U and Th concentration in the olivines to be about 1 ppb and 0.1 ppb respectively, corresponding to apparent DUol/melt and DThol/melt of 0.003 and 0.0001 if host lave has U of 0.3 ppm and Th of 1ppm (Gayer et al.,2008). Recently, helium isotopic measurements were made in these olivines (Gayer et al., 2008) and the results yield a basin-wide average erosion rate of 0.056 mma-1 for Waimea river watershed. Gayer et al. (2008) argued that

  2. Diffusion of highly charged cations in olivine

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Diffusion of tungsten, titanium and phosphorus have been measured in natural iron-bearing olivine (~Fo90) and synthetic forsterite. Experiments were run under buffered conditions (with iron-wustite or Ni-NiO buffers) in 1-atm furnaces. The sources of diffusant for experiments were MgWO4 for tungsten diffusion, Mg2TiO4 for Ti diffusion, and AlPO4 for P diffusion; in all cases these compounds were pre-reacted at high temperature with Mg2SiO4 or Fe-bearing olivine prior to diffusion anneals. Samples were placed with the source materials in noble metal or silica capsules, which were sealed under vacuum in silica glass ampoules with solid buffers. Rutherford backscattering spectrometry (RBS) was used to measure depth profiles for all sets of experiments; measurements of P were also made with Nuclear Reaction Analysis using the 31P(α,p)34S reaction. These new data suggest marked differences among diffusivities of these cations, with titanium diffusion faster than diffusion of tungsten, but slower than diffusion of phosphorus over the conditions investigated. Diffusivities of all of these elements appear significantly slower than those of divalent cations in olivine. These results will be discussed in context with extant diffusion data for major, trace and minor elements in olivine. The effects of oxygen fugacity and olivine composition on diffusion, and potential implications for diffusion mechanisms will also be considered.

  3. Olivines: revelation of tracks of charged particles.

    PubMed

    Krishnaswami, S; Lal, D; Prabhu, N; Tamhane, A S

    1971-10-15

    A one-step, three-component aqueous etchant was developed for revealing the tracks of charged particles in olivine. The etchant reveals tracks of small cone angle, which are equally well developed in all the crystallographic directions. The scope of fossil cosmic-ray track studies in extraterrestrial samples has thus been increased, because olivine is often an abundant constituent and because it has a higher threshold ionization for track registration and has lower uranium, thorium, and trace element concentrations as compared with pyroxenes and feldspars. The etchant does not attack any of the principal rock-forming minerals in normal etching time, which allows a nondestructive study of fossil tracks in thin-section mounts. The study of fossil cosmic-ray tracks in olivine is particularly valuable for investigations of very, very heavy cosmic-ray nuclei and for highly irradiated samples such as those found in the lunar regolith. PMID:17778062

  4. Olivine-FeS Partial-Melt

    SciTech Connect

    Roberts, J; Siebert, J; Ryerson, F J; Kinney, J

    2006-10-02

    The figure shows Fe-S-filled melt channels in olivine created at high temperature and pressure. The 3D image was obtained on Beamline 8.3.2 at the Advanced Light Source, Lawrence Berkeley Laboratory, with a spatial resolution of better than two microns (bar is 10 microns). Permeability of Fe-S melts in olivine at high temperatures and pressures provides an important constraint on models of planetary core formation. Permeability must be inferred from empirical relationships based on microstructure. To date, estimates of permeability have varied by more than five orders of magnitude. To provide more accurate constraints, we used high-resolution synchrotron radiation computed tomography to image the three-dimensional network of melt-containing pores in an olivine matrix, and calculated the permeability directly by solving the equations of Stokes flow through the actual pore network using a lattice-Boltzmann approach. These calculations provide an independent constraint on models of planetary core formation.

  5. 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.

  6. 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.

  7. Water-induced fabric transitions in olivine.

    PubMed

    Jung, H; Karato S

    2001-08-24

    The interpretation of seismic anisotropy in Earth's upper mantle has traditionally been based on the fabrics (lattice-preferred orientation) of relatively water-poor olivine. Here we show that when a large amount of water is added to olivine, the relation between flow geometry and seismic anisotropy undergoes marked changes. Some of the puzzling observations of seismic anisotropy in the upper mantle, including the anomalous anisotropy in the central Pacific and the complicated anisotropy in subduction zones, can be attributed to the enrichment of water in these regions. PMID:11520979

  8. The origin of ferrous zoning in Allende chondrule olivines

    NASA Astrophysics Data System (ADS)

    Peck, J. A.; Wood, J. A.

    1987-06-01

    Very similar major and minor element compositions are noted in the ferrous olivine occurring in chondrules at olivine grain boundaries, along cracks in olivine grains, interleaved with enstatite, and in the inner portions of exposed olivine grain surface rims; simultaneous formation by a single process is therefore suggested. The ferrous chondrule olivine probably formed by the reaction of chondrules with very hot nebular vapors over a period of several hours, followed by the condensation of residual metal vapors onto those olivine surfaces that were in direct contact with the gas as the system cooled. The ferrous chondrule olivine that occurs interleaved with enstatite in Allende does not have a composition identical to, and is not the precursor of, matrix olivine.

  9. Defect chemistry of phospho-olivine nanoparticles synthesized by a microwave-assisted solvothermal process

    NASA Astrophysics Data System (ADS)

    Bridges, Craig A.; Harrison, Katharine L.; Unocic, Raymond R.; Idrobo, Juan-Carlos; Parans Paranthaman, M.; Manthiram, Arumugam

    2013-09-01

    Nanocrystalline LiFePO4 powders synthesized by a microwave-assisted solvothermal (MW-ST) process have been structurally characterized with a combination of high resolution powder neutron diffraction, synchrotron X-ray diffraction, and aberration-corrected HAADF STEM imaging. A significant level of defects has been found in the samples prepared at 255 and 275 °C. These temperatures are significantly higher than what has previously been suggested to be the maximum temperature for defect formation in LiFePO4, so the presence of defects is likely related to the rapid MW-ST synthesis involving a short reaction time (˜5 min). A defect model has been tentatively proposed, though it has been shown that powder diffraction data alone cannot conclusively determine the precise defect distribution in LiFePO4 samples. The model is consistent with other literature reports on nanopowders synthesized at low temperatures, in which the unit cell volume is significantly reduced relative to defect-free, micron-sized LiFePO4 powders.

  10. 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.

  11. 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

  12. 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

  13. Shock-produced olivine glass: First observation

    USGS Publications Warehouse

    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, (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.

  14. H in olivine: How much and where?

    NASA Astrophysics Data System (ADS)

    Withers, A. C.; Umemoto, K.; Hirschmann, M. M.

    2011-12-01

    Hydrous defects in nominally anhydrous minerals are known to play a fundamental role in influencing the mechanisms and extent of deformation in mantle rocks. The extent of water weakening in olivine, in particular, may dictate the nature of upper mantle deformation, thereby controlling the very processes of tectonism. Infrared spectroscopy (IR) is a powerful tool commonly used to analyze these extrinsic defects. In addition to determining defect concentrations, and in contrast to other analytical techniques such as secondary ion mass spectroscopy (SIMS), IR offers the possibility of determining the location of H atoms in the crystal structure. In the case of olivine, however, the relationships between the IR spectrum and the concentrations and locations of hydrous defects are widely disputed, with recent estimates of calibration coefficients varying by more than a factor of 3, and the same absorption bands being thought variously to represent substitutions on tetrahedral or on octahedral crystallographic sites. New analytical and theoretical results will be used to refine our view of the location and concentration of H in olivine. Elastic recoil detection analysis (ERDA) measurements are used to determine the infrared absorption coefficient (k) for OH bands in Fo90 olivines with 240-2000 ppm H2O, synthesised at 3-10 GPa in multianvil experiments that were optimised for growth of large, homogeneous crystals. On the basis of 20 ERDA and >200 FTIR analyses of olivines from 7 experiments, the H content (in ppm H2O) is given by 0.120±0.008×total integral absorption, corresponding to an integral extinction coefficient of 45,000 L/(mol cm2), i.e. k is ~35% smaller than the value previously derived by Bell et al. (2003)[1] for natural olivines. This implies that the H contents of experimental olivines have been generally overestimated. The samples that were analysed using ERDA are used as SIMS standards, thereby providing a direct calibration that avoids the baseline

  15. 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.

  16. 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

  17. 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.

  18. Search for Olivine Spectral Signatures on the Surface of Vesta

    NASA Technical Reports Server (NTRS)

    Palomba, E.; De Sanctis, M. C.; Ammannito, E.; Capaccioni, F.; Capria, M. T.; Farina, M.; Frigeri, A.; Longobardo, A.; Tosi, F.; Zambon, F.; McSween, H. Y.; Mittlefehldt, D. W.; Russell, C. T.; Raymond, C. A.; Sunshine, J.; McCord, T. B.

    2012-01-01

    The occurrence of olivines on Vesta were first postulated from traditional petrogenetic models which suggest the formation of olivine as lower crustal cumulates. An indirect confirmation is given by their presence as a minor component in some samples of diogenite meteorites, the harzburgitic diogenites and the dunitic diogenites, and as olivine mineral clasts in howardites. Another indication for this mineral was given by interpretations of groundbased and Hubble Space Telescope observations that suggested the presence of local olivine-bearing units on the surface of Vesta. The VIR instrument onboard the DAWN mission has been mapping Vesta since July 2011. VIR acquired hyperspectral images of Vesta s surface in the wavelength range from 0.25 to 5.1 m during Approach, Survey and High Altitude Mapping (HAMO) orbits that allowed a 2/3 of the entire asteroid surface to be mapped. The VIR operative spectral interval, resolution and coverage is suitable for the detection and mapping of any olivine rich regions that may occur on the Vesta surface. The abundance of olivine in diogenites is typically lower than 10% but some samples richer in olivine are known. However, we do not expect to have extensive exposures of olivine-rich material on Vesta. Moreover, the partial overlap of olivine and pyroxene spectral signatures will make olivine difficult to detect. Different spectral parameters have been used to map olivine on extraterrestrial bodies, and here we discuss the different approaches used, and develop new ones specifically for Vesta. Our new methods are based on combinations of the spectral parameters relative to the 1 and 2 micron bands (the most prominent spectral features of Vesta surface in the visible and the infrared), such as band center locations, band depths, band areas, band area ratios. Before the direct application to the VIR data, the efficiency of each approach is evaluated by means of analysis of laboratory spectra of HED meteorites, pyroxenes, olivines

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. Olivine diogenites - The mantle of the eucrite parent body

    NASA Technical Reports Server (NTRS)

    Sack, Richard O.; Azeredo, William J.; Lipschutz, Michael E.

    1991-01-01

    Two olivine-rich Antarctic diogenites (ALH A77256 and ALH 84001) of the howardite-eucrite-diogenite (HED) meteorite association have olivine/pyroxene ratios similar to normative ratios in devolatilized ordinary chondrites. Based on chemical data and petrological analysis, these meteorites represent the residuum of partial melting of the mantle in the eucrite parent body (EPB). Mineral assemblages in these olivine-rich diogenites record a continuum in thermal histories from initial partial melting (1150-1200 C) to subsolidus reequilibration (795 + or - 55 C). The small number of olivine-rich diogenites known hints that only the outer portion of the EPB has been sampled.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. Development of crystal preferred orientation of olivine during diffusion creep: a matter of olivine crystal shape

    NASA Astrophysics Data System (ADS)

    Miyazaki, T.; Sueyoshi, K.; Hiraga, T.

    2013-12-01

    Crystalloagraphic preferred orientation (CPO) of olivine produced during dislocation creep is considered the primary cause of elastic anisotropy in the upper mantle of Earth and is used by seismologists to determine the direction of flow. Here we show that synthetic Fe-free olivine aggregates with either diopside or melt develop strong to weak CPO during grain boundary sliding (GBS) accommodated by diffusion. GBS on boundaries that correspond to specific crystallographic planes produces CPO. By combining the CPO patterns developed during tension and compression experiments, we predict formation in the mantle of three different CPO patterns depending on temperature and the presence of melt. Strong radial anisotropy is anticipated for GBS accommodated by diffusion during simple shear deformation at temperatures from 0.92*Ts to Ts (Ts: solidus temperature). These conditions correspond to depths where melting initiates to 50-100 km deeper and where strongly anisotropic and low seismic velocities are detected.

  10. 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.

  11. 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.

  12. Remote Compositional Analyses of Lunar Olivine-Bearing Lithologies

    NASA Astrophysics Data System (ADS)

    Isaacson, P.; Clark, R. N.; Head, J. W.; Klima, R.; Petro, N. E.; Pieters, C. M.; Staid, M.; Sunshine, J. M.; Taylor, L. A.; Thaisen, K. G.; Tompkins, S.

    2009-12-01

    The Moon Mineralogy Mapper (M3) is a guest instrument on Chandrayaan-1, India’s first mission to the Moon. M3 is an imaging spectrometer covering the wavelength range of 430 nm - 3000 nm, and was designed to map the mineralogy of the lunar surface. The high spectral resolution of M3 enables the diagnostic absorption features of lunar minerals to be identified clearly, while the high spatial resolution of M3 allows the identification and mapping of distinct lithologic units. Olivine is an important mineral with which to interpret the petrologic evolution of igneous rocks. The composition of olivine (Mg#) is used to indicate the degree of evolution of the source magma from which a sample crystallized. Visible to near-infrared reflectance spectroscopy is sensitive to the Mg# of olivine, as the diagnostic olivine absorption features shift in response to changing major element abundances (Mg and Fe) content. These changes in diagnostic absorption features can be detected by modeling the individual absorption bands with the Modified Gaussian Model (MGM). Spectra of lunar olivines differ from spectra of their terrestrial and synthetic counterparts due to the inclusions of Cr-spinel common to lunar olivines; however, analysis of lunar olivine mineral separates in terrestrial laboratories and modeling of the resulting reflectance spectra have been able to unravel the chromite effects on the olivine spectrum. Previous efforts at remote compositional analysis of lunar olivine have been limited by spectral resolution and coverage or by spatial resolution. However, the spatial and spectral resolution provided by M3 enable olivine composition to be determined remotely in a spatial context. We are in the process of identifying olivine-bearing lithologies on the lunar farside and analyzing the olivine composition with the modified MGM approach. Initial compositional analyses have been completed for a crater on the rim of the Moscoviense basin that appears to be largely dominated

  13. 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

  14. 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

  15. Mineralogy of interplanetary dust particles from the 'olivine' infrared class

    NASA Technical Reports Server (NTRS)

    Christoffersen, R.; Buseck, P. R.

    1986-01-01

    Analytical electron microscopy observations establish that olivine is abundant and the predominant silicate phase in three interplanetary dust particles (IDPs) from the 'olivine' infrared spectra category. Two of the particles have microstructures resembling those of most nonhydrous chondritic IDPs, consisting of micron to submicron grains together with a matrix composed of amorphous carbonaceous material and sub-500 A grains. In addition to olivine these particles respectively contain enstatite and magnetite, and pentlandite plus Ca-rich clinopyroxene. The third IDP consists mostly of olivine and pyrrhotite with little or no matrix material. Olivine grains in this particle contain prominent solar-flare ion tracks with densities corresponding to a space-exposure age between 1000 to 100,000 years. Although the three particles have olivine-rich mineralogies in common, other aspects of their mineralogies and microstructures suggest that they experienced different formation histories. The differences between the particles indicate that the olivine infrared spectral category is a diverse collection of IDPs that probably incorporates several genetic groups.

  16. The olivine macrocryst problem: New insights from minor and trace element compositions of olivine from Lac de Gras kimberlites, Canada

    NASA Astrophysics Data System (ADS)

    Bussweiler, Yannick; Foley, Stephen F.; Prelević, Dejan; Jacob, Dorrit E.

    2015-04-01

    This study presents detailed petrographical and geochemical investigations on remarkably fresh olivines in kimberlites from the EKATI Diamond Mine™ located in the Tertiary/Cretaceous Lac de Gras kimberlite field within the Slave craton of Canada. Olivine, constituting about 42 vol.% of the analyzed samples, can be divided into two textural groups: (i) macrocrystic olivines, > 100 μm sub-rounded crystals and (ii) groundmass olivines, < 100 μm subhedral crystals. Olivines from both populations define two distinct chemical trends; a "mantle trend" with angular cores, showing low Ca (< 0.1 wt.% CaO) and high Ni (0.3-0.4 wt.% NiO) at varying Mg# (0.86-0.93), contrasts with a "melt trend" typified by thin (< 100 μm) rims with increasing Ca (up to 1.0 wt.% CaO) and decreasing Ni (down to 0.1 wt.% NiO) contents at constant Mg# (~ 0.915). These findings are in agreement with recent studies suggesting that virtually all olivine is composed of xenocrystic (i.e. mantle-related) cores with phenocrystic (i.e. melt-related) overgrowths, thereby challenging the traditional view that the origin of kimberlitic olivine can be distinguished based on size and morphology. The two main trends can be further resolved into sub-groups refining the crystallization history of olivine; the mantle trend indicates a multi-source origin that samples the layered lithosphere below the Slave craton, whereas the melt trend represents multi-stage crystallization comprising a differentiation trend starting at mantle conditions and a second trend controlled by the crystallization of additional phases (e.g. chromite) and changing magma conditions (e.g. oxidation). These trends are also seen in the concentrations of trace elements not routinely measured in olivine (e.g. Na, P, Ti, Co, Sc, Zr). Trace element mapping with LA-ICP-MS reveals the distribution of these elements within olivine grains. The trace element distribution between the two trends appears to be consistent with phenocrystic olivine

  17. 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.

  18. 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.

  19. 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.

  20. Detection of new olivine-rich locations on Vesta

    NASA Astrophysics Data System (ADS)

    Palomba, Ernesto; Longobardo, Andrea; De Sanctis, Maria Cristina; Zinzi, Angelo; Ammannito, Eleonora; Marchi, Simone; Tosi, Federico; Zambon, Francesca; Capria, Maria Teresa; Russell, Christopher T.; Raymond, Carol A.; Cloutis, Edward A.

    2015-09-01

    The discovery of olivine on Vesta's surface by the VIR imaging spectrometer onboard the Dawn space mission has forced us to reconsider our views of Vestan petrogenetic models. Olivines were expected to be present in the interior of Vesta: in the mantle of a vertically layered body as invoked by the magma ocean models, or at the base (or within) the mantle-crust boundary as proposed by fractionation models. Olivines have been detected by VIR-Dawn in two wide areas near Arruntia and Bellicia, regions located in the northern hemisphere. Interestingly, these olivine-rich terrains are far from the Rheasilvia and the more ancient Veneneia basins, which are expected to have excavated the crust down to reach the mantle. In this work we present our attempts to identify other undetected olivine rich areas on Vesta by using spectral parameters sensitive to olivine such as the Band Area Ratio (BAR) and other specific parameters created for the detection of olivines on Mars (forsterite, fayalite and a generic olivine index). As a preliminary step we calibrated these parameters by means of VIS-IR spectra of different HED meteorite samples: behaviors versus sample grain size and albedo were analyzed and discussed. We selected the BAR and the Forsterite Index as the best parameters that can be used on Vesta. A cross-correlation analysis has been applied in order to detect olivine signature on the VIR hyperspectral cubes. These detections have then been confirmed by an anti-correlation analysis between the BAR and one of the olivine parameters, independent of the first method applied. In agreement with the recent discovery, Arruntia and Bellicia were found to be as the most olivine-rich areas, i.e. where the parameter values are strongest. In addition we detected 6 new regions, all but one located in the Vesta north hemisphere. This result confirms again that the old petrogenetic models cannot be straightforwardly applied to Vesta and should be reshaped in the view of these new

  1. 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.

  2. Dislocation creep of fine-grained olivine

    NASA Astrophysics Data System (ADS)

    Faul, U. H.; Fitz Gerald, J. D.; Farla, R. J. M.; Ahlefeldt, R.; Jackson, I.

    2011-01-01

    Deformation experiments conducted in a gas medium apparatus at temperatures from 1200 to 1350°C with a fine-grained, solution-gelation derived Fe-bearing olivine show a stress dependence of the strain rate at stresses above ˜150 MPa, which is much stronger than previously reported for polycrystalline samples. The data can be fit by a power law with ??σn with n ˜ 7-8, or equally well by a Peierls creep law with exponential stress dependence. Due to the observed strong stress dependence the samples deform at significantly higher strain rates at a given stress than single crystals or coarse-grained polycrystals with n ˜ 3.5. TEM observations indicate the presence of dislocations with at least two different Burgers vectors, with free dislocations predominantly of screw character. Subgrain walls are present but are only weakly developed and have small misorientation angles. Both the rheology and dislocation structures are consistent with creep rate-limited by dislocation glide or cross slip for aggregates with grain sizes smaller than or approaching the recrystallized grain size. Deformation mechanism maps extrapolated to lithospheric temperatures using the melt-free diffusion creep rheology of Faul and Jackson (2007), the dislocation creep rheology of Hirth and Kohlstedt (2003), and the results described here indicate that deformation conditions of ultramylonitic shear zones fall near the triple point of Peierls, dislocation, and diffusion creep.

  3. 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.

  4. 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.

  5. Applications of dynamic crystallization studies - Lunar olivine-normative basalts

    NASA Technical Reports Server (NTRS)

    Bianco, A. S.; Taylor, L. A.

    1977-01-01

    Dynamic crystallization studies were performed on two synthetic glasses similar in composition to the mare olivine-normative basalt samples 12009 and 15555. The effects of viscosity (primarily a function of FeO) and the initial temperature of cooling on mineral chemistry, texture, and temperature of appearance of phases were investigated. Olivine compositions seem to indicate that, for the two types of melt cooled at the same rate, there are no significant differences in the degree of undercooling at which olivine nucleates, but it is found that olivine-nucleated densities differ. The cooling rate of 15555 is estimated. Since the temperature at which cooling is initiated affects texture, mineral chemistry, and temperature of appearance of phases so greatly, caution is recommended in the application of experimental data to natural rock systems.

  6. 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.

  7. 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.

  8. The Microstructure of a Micrometeorite Impact into Lunar Olivine

    NASA Astrophysics Data System (ADS)

    Noble, S. K.; Keller, L. P.; Christoffersen, R.; Rahman, Z.

    2015-11-01

    Through TEM analysis of the cross-section of a ~20 µm diameter crater into an olivine single crystal we can see first-hand the effects of a single impact, including the creation of nanophase iron in the melt.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. Olivine and pyroxene from the mantle of asteroid 4 Vesta

    NASA Astrophysics Data System (ADS)

    Lunning, Nicole G.; McSween, Harry Y.; Tenner, Travis J.; Kita, Noriko T.; Bodnar, Robert J.

    2015-05-01

    A number of meteorites contain evidence that rocky bodies formed and differentiated early in our solar system's history, and similar bodies likely contributed material to form the planets. These differentiated rocky bodies are expected to have mantles dominated by Mg-rich olivine, but direct evidence for such mantles beyond our own planet has been elusive. Here, we identify olivine fragments (Mg# = 80-92) in howardite meteorites. These Mg-rich olivine fragments do not correspond to an established lithology in the howardite-eucrite-diogenite (HED) meteorites, which are thought to be from the asteroid 4 Vesta; their occurrence in howardite breccias, combined with diagnostic oxygen three-isotope signatures and minor element chemistry, indicates they are vestan. The major element chemistry of these Mg-rich olivines suggests that they formed as mantle residues, in crustal layered intrusions, or in Mg-rich basalts. The trace element chemistry of these Mg-rich olivines supports an origin as mantle samples, but other formation scenarios could be possible. Interpreted as mantle samples, the range of Mg-rich olivine compositions indicates that Vesta's structure differs from that predicted by conventional models: Vesta has a chemically heterogeneous mantle that feeds serial magmatism. The range of olivine major element chemistries is consistent with models of an incompletely melted mantle such as in the model proposed by Wilson and Keil (2013) rather than a whole-mantle magma ocean for Vesta. Trace element chemistries of Mg-rich pyroxenes (Mg# = 85-92) provide support that some of these pyroxenes may represent initial fractional crystallization of mantle partial melts.

  14. Grain boundary diffusion in olivine (Invited)

    NASA Astrophysics Data System (ADS)

    Marquardt, K.; Dohmen, R.

    2013-12-01

    Olivine is the main constituent of Earth's upper mantle. The individual mineral grains are separated by grain boundaries that have very distinct properties compared to those of single crystals and strongly affect large-scale physical and chemical properties of rocks, e.g. viscosity, electrical conductivity and diffusivity. Knowledge on the grain boundary physical and chemical properties, their population and distribution in polycrystalline materials [1] is a prerequisite to understand and model bulk (rock) properties, including their role as pathways for element transport [2] and the potential of grain boundaries as storage sites for incompatible elements [3]. Studies on selected and well characterized single grain boundaries are needed for a detailed understanding of the influence of varying grain boundaries. For instance, the dependence of diffusion on the grain boundary structure (defined by the lattice misfit) and width in silicates is unknown [2, 4], but limited experimental studies in material sciences indicate major effects of grain boundary orientation on diffusion rates. We characterized the effect of grain boundary orientation and temperature on element diffusion in forsterite grain boundaries by transmission electron microscopy (TEM).The site specific TEM-foils were cut using the focused ion beam technique (FIB). To study diffusion we prepared amorphous thin-films of Ni2SiO4 composition perpendicular to the grain boundary using pulsed laser deposition. Annealing (800-1450°C) leads to crystallization of the thin-film and Ni-Mg inter-diffuse into the crystal volume and along the grain boundary. The inter-diffusion profiles were measured using energy dispersive x-ray spectrometry in the TEM, standardized using the Cliff-Lorimer equation and EMPA measurements. We obtain volume diffusion coefficients that are comparable to Ni-Mg inter-diffusion rates in forsterite determined in previous studies at comparable temperatures, with similar activation energies

  15. A Method for the Flux Growth of Intermediate Composition Olivine

    NASA Astrophysics Data System (ADS)

    Deangelis, M. T.; Anovitz, L. M.; Labotka, T. C.; Frederick, D. A.

    2009-05-01

    Though solid solution of iron and magnesium between forsterite (Mg2SiO4) and fayalite (Fe2SiO4) is possible in the olivine crystal structure, the high oxygen fugacity condition of the terrestrial mantle inhibits the widespread crystallization of intermediate (Fo40-Fo60) composition olivine. This limitation is not the same for some other inner solar system bodies (e.g. the Moon and Mars), where conditions are reducing and olivine compositions are wide ranging. Unfortunately, the amount of samples from the Moon and Mars is extremely limited; with only Apollo and Luna mission samples, lunar meteorites, and Martian meteorites available for direct mineralogic and petrologic characterization. These characterizations have provided a useful basis for many spectroscopic and modeling interpretations, but many fundamental questions remain and may only be answerable through either direct observation of rocks or by analog experimentation. The motivation for our work on growth of intermediate olivine crystals, therefore, is to create realistic starting material for use in Mars and Moon analog experiments. A variety of crystal growth methods have been previously used to synthesize olivine, including: the Czochralski-pulling (CZ) method, the floating-zone image furnace (FZ) method, and sol-gel processing techniques. Both the CZ and FZ methods have the advantage of producing large crystals, but the growth apparatus and regulation of reduced atmospheric conditions during growth can make these techniques both time and cost intensive. Sol-gel processing to produces olivine fibers is a useful chemical technique, but obtaining larger grain sizes can be difficult. An alternative method for crystal growth is through the use a flux, which can grow crystals relatively quickly and inexpensively. We have grown synthetic crystals of intermediate composition (Fo30-Fo70) olivine using a lithium borate (B5Li3O9) flux. The starting material was a mixture of magnesite (MgCO3), siderite (FeCO3), and

  16. 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

  17. 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.

  18. B-type Olivine Fabric induced by Grain Boundary Sliding

    NASA Astrophysics Data System (ADS)

    Précigout, Jacques; Hirth, Greg

    2013-04-01

    Olivine fabric, or Lattice Preferred Orientation (LPO), in naturally deformed peridotite largely contributes to the seismic anisotropy of the upper mantle. LPO usually results from motion of intra-crystalline dislocations during dislocation creep. In this case, experimental and numerical data indicate that the degree of mineral alignment (fabric strength) increases with increasing finite strain. Here, we show an opposite trend suggesting that olivine fabric can also result from a different deformation mechanism. Based on documentation of olivine LPOs in peridotites of a kilometer-scale mantle shear zone in the Ronda massif (Spain), we highlight a transition from a flow-parallel [a]- axis LPO (A-type fabric) to a flow-normal [a]-axis LPO (B-type fabric). While dislocation sub-structures indicate that A-type fabric results from dislocation motion, we conclude that the B-type fabric does not originate from dislocation creep, but instead from grain boundary sliding (GBS) because: (1) dislocation sub-structures remain consistent with the A-type slip system in all samples; (2) the fabric transition from A-type to B-type correlates with decreasing fabric strength despite increasing finite strain; and (3) our observations are supported by experiments that document B-type fabric in olivine aggregates where deformation involves a component of GBS. The B-type olivine fabric has a specific signature in term of seismic anisotropy, and hence, our results may have important implications for interpreting upper mantle structures and deformation processes via seismic observations.

  19. Martian dunite NWA 2737: Integrated spectroscopic analyses of brown olivine

    NASA Astrophysics Data System (ADS)

    Pieters, Carle M.; Klima, Rachel L.; Hiroi, Takahiro; Dyar, M. Darby; Lane, Melissa D.; Treiman, Allan H.; Noble, Sarah K.; Sunshine, Jessica M.; Bishop, Janice L.

    2008-06-01

    A second Martian meteorite has been identified that is composed primarily of heavily shocked dunite, Northwest Africa (NWA) 2737. This meteorite has several similarities to the Chassigny dunite cumulate, but the olivine is more Mg rich and, most notably, is very dark and visually brown. Carefully coordinated analyses of NWA 2737 whole-rock and olivine separates were undertaken using visible and near-infrared reflectance, midinfrared emission and reflectance, and Mössbauer spectroscopic studies of the same samples along with detailed petrography, chemistry, scanning electron microscopy, and transmission electron microscopy analyses. Midinfrared spectra of this sample indicate that the olivine is fully crystalline and that its molecular structure remains intact. The unusual color and spectral properties that extend from the visible through the near-infrared part of the spectrum are shown to be due to nanophase metallic iron particles dispersed throughout the olivine during a major shock event on Mars. Although a minor amount of Fe3+ is present, it cannot account for the well-documented unusual optical properties of Martian meteorite NWA 2737. Perhaps unique to the Martian environment, this ``brown'' olivine exhibits spectral properties that can potentially be used to remotely explore the pressure-temperature history of surface geology as well as assess surface composition.

  20. Minor elements in lunar olivine as a petrologic indicator

    NASA Technical Reports Server (NTRS)

    Steele, I. M.; Smith, J. V.

    1975-01-01

    Accurate electron microprobe analyses (approximately 50 ppm) were made for Al, Ca, Ti, Cr, Mn, and Ni in Mg-rich olivines which may derive from early lunar crust or deeper environments. Low-Ca contents consistently occur only in olivines from dunitic and troctolitic breccia: spinel troctolite and other rock types have high-Ca olivines suggesting derivation by near-surface processes. Rock 15445 has olivine with distinctly low CaO (approximately 0.01 wt.%). Chromium ranges to higher values (max.0.2 oxide wt.%) than for terrestrial harzburgites and lherzolites but is similar to the range in terrestrial komatiites. Divalent chromium may be indicated over trivalent Cr because olivines lack sufficient other elements for charge balance of the latter. NiO values in lunar specimens range from 0.00 to 0.07 wt.% and a weak anticorrelation with Cr2O3 suggests an oxidation state effect. Al2O3 values are mostly below 0.04-wt.% and show no obvious correlation with fragment type. TiO2 values lie below 0.13-wt.% and seem to correlate best with crystallization rate and plagioclase content of the host rock. High values of Al2O3 and TiO2 reported by other workers have not been confirmed, and are probably wrong.

  1. 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.

  2. Effect of Mineralogy on the Rheological Properties of Olivine, Othopyroxene and Olivine/Orthopyroxene Mixtures at High Temperature and Pressure

    NASA Astrophysics Data System (ADS)

    Homburg, J. M.; Mei, S.; Kohlstedt, D. L.

    2013-12-01

    To better understand the influence of mineralogy on the rheological properties of the upper mantle, we have carried out a series of triaxial compressive creep experiments on olivine/orthopyroxene mixtures under high pressures (~6 GPa) and high temperatures (1373 - 1473 K) under anhydrous conditions. Experiments were performed using the deformation-DIA (D-DIA) apparatus on beamline X17B2 at the National Synchrotron Light Source at Brookhaven National Laboratory. Samples of three mineralogical compositions (olivine, orthopyroxene and 50:50 volumetric ratio of olivine:orthopyroxene) were prepared from fine-grained (~10 μm) mineral separates of San Carlos olivine and orthopyroxene. Orthopyroxene and olivine/orthopyroxene samples were cold pressed to attain a cylinder ~1 mm in length and 1.1 mm in diameter. The cold pressed sample was then stacked with a hot-pressed olivine sample of similar size and assembled with alumina pistons, a boron nitride sleeve and graphite resistance heater into a 6.2-mm edge length cubic pressure medium. Nickel disks were placed at the ends of both samples to act as strain markers. During each experiment, in-situ stress and strain measurements were obtained from X-ray diffraction and radiography, respectively. After annealing the samples at the pressure/temperature conditions of deformation for ~2 hours to insure compaction of the cold pressed sample, experiments were conducted at constant strain rates between 2.2x10^-5 and 3.3x10^-5 s^-1 up to axial strains of 5 to 20%. The orthopyroxene and olivine/orthopyroxene mixture deformed at approximately the same rate with the mixed phase system displaying some weakening relative to the single-phase system. This observation suggests that orthopyroxene may be controlling sample behavior in the mixed phase material. In contrast, the orthopyroxene and olivine/orthopyroxene samples crept ~ 2 - 3 times faster than olivine. This contrast in rheological behavior was observed at lower temperatures

  3. 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

  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. The identification of crystalline olivine in cometary silicates

    NASA Technical Reports Server (NTRS)

    Campins, Humberto; Ryan, Eileen V.

    1989-01-01

    An intermediate-resolution spectrum of the 8-13 micron region in comet Halley is obtained which shows a prominent silicate emission feature with structure not observed before in other comets or in interstellar silicates. The presence of a strong 11.3 micron peak reported by Bregman and coworkers is confirmed, and evidence is found for additional structure in the band. By comparison with spectra of interplanetary dust particles and laboratory silicates, it is concluded that small crystalline olivine particles are a major component of the silicates in this comet; other silicates (e.g., amorphous or hydrated) must also be present. The identification of crystalline olivine in this part of the spectrum is supported by the observation of four peaks in 20-50 micron airborne spectra of this comet which have also been attributed to olivine.

  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. The identification of crystalline olivine in cometary silicates

    NASA Astrophysics Data System (ADS)

    Campins, H.; Ryan, E. V.

    1989-06-01

    An intermediate-resolution spectrum of the 8-13 micron region in comet Halley is obtained which shows a prominent silicate emission feature with structure not observed before in other comets or in interstellar silicates. The presence of a strong 11.3 micron peak reported by Bregman and coworkers is confirmed, and evidence is found for additional structure in the band. By comparison with spectra of interplanetary dust particles and laboratory silicates, it is concluded that small crystalline olivine particles are a major component of the silicates in this comet; other silicates (e.g., amorphous or hydrated) must also be present. The identification of crystalline olivine in this part of the spectrum is supported by the observation of four peaks in 20-50 micron airborne spectra of this comet which have also been attributed to olivine.

  8. Thermal Emission Spectroscopy of 1 Ceres: Evidence for Olivine

    NASA Technical Reports Server (NTRS)

    Witteborn, Fred. C.; Roush, Ted L.; Cohen, Martin

    1999-01-01

    Thermal emission spectra of the largest asteroid, 1 Ceres, obtained from the Kuiper Airborne Observatory display features that may provide information about its surface mineralogy. The emissivity, obtained by dividing the spectra by a standard thermal model, is compared with emissivity spectra of olivines and phyllosilicates deduced via Kirchoff's law from reflectivity measurements. The spectra provide a fairly good match to fine grained olivines (0 to 5 micrometer size range). The smoothness of the spectrum beyond 18 micrometers is an indication of particles smaller than 50 micrometers. While the abrupt rise in emissivity near 8 micrometers matches many silicates, the distinct emissivity minimum centered near 12.8 micrometers is consistant with iron-poor olivines, but not with phyllosilicates. It suggests the presence of opaques and does not exclude a mixture with organics and fine-grained phyllosilicates.

  9. 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

  10. 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.

  11. 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.

  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. 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.

  14. Water Retention and Rheology of Ti-doped, Synthetic Olivine

    NASA Astrophysics Data System (ADS)

    Faul, U.; Jackson, I.; Fitz Gerald, J. D.

    2012-12-01

    Upper mantle flow laws are currently based almost entirely on experiments with olivine from San Carlos in Arizona. Synthetically produced olivine enables the exploration of the effects of trace elements on the rheology. We have conducted a range of experiments in a gas medium apparatus with solution-gelation derived olivine that show that titanium is the most effective in binding water in the olivine structure. The FTIR signature of this structurally bound water is most similar to that of water-undersaturated natural olivine with absorption bands at 3575 and 3525 cm-1. Water added, titanium-free solgel contains little water after hotpressing and shows adsorption bands at wavenumbers near 3200 cm-1. Noble metal capsules such as Pt or AuPd, providing more oxidizing conditions, are more effective in retaining water. Experiments with NiFe-lined welded Pt capsules retain no more water than NiFe lined samples without Pt capsule. Water retention is, however, again dependent on trace element content, with Ti doped samples containing tens of ppm after hotpressing. By comparison undoped samples run under the same conditions contain little water, again with different FTIR spectra to Ti-doped samples. Our experiments suggest that Ti by itself, or with water contents at the FTIR detection limit enhances diffusion creep rates relative to undoped, dry solgel olivine. Water contents around 10 ppm in NiFe wrapped samples show an enhancement of strain rates of more than one order of magnitude. The addition of Ti, together with the presence of water, also enhances grain growth. For more coarse-grained samples in the dislocation creep regime the enhancement of the stain rate as a function of water content is approximately consistent with the flow laws of Hirth and Kohlstedt (2003).

  15. 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

  16. 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.

  17. 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.

  18. Factors affecting the direct mineralization of CO2 with olivine.

    PubMed

    Kwon, Soonchul; Fan, Maohong; DaCosta, Herbert F M; Russell, Armistead G

    2011-01-01

    Olivine, one of the most abundant minerals existing in nature, is explored as a CO2 carbonation agent for direct carbonation of CO2 in flue gas. Olivine based CO2 capture is thermodynamically favorable and can form a stable carbonate for long-term storage. Experimental results have shown that water vapor plays an important role in improving CO2 carbonation rate and capacities. Other operation conditions including reaction temperature, initial CO2 concentration, residence time corresponding to the flow rate of CO2 gas stream, and water vapor concentration also considerably affect the performance of the technology. PMID:22128528

  19. 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

  20. 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.

  1. Trace Element Compositions of Pallasite Olivine Grains and Pallasite Origin

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, David W.; Herrin, J. S.

    2010-01-01

    Pallasites are mixtures of metal with magnesian olivine. Most have similar metal compositions and olivine oxygen isotopic compositions; these are the main-group pallasites (PMG). The Eagle Station grouplet of pallasites (PES) have distinctive metal and olivine compositions and oxygen isotopic compositions. Pallasites are thought to have formed at the core-mantle boundary of their parent asteroids by mixing molten metal with solid olivine of either cumulatic or restitic origin. We have continued our investigation of pallasite olivines by doing in situ trace element analyses in order to further constrain their origin. We determined Al, P, Ca, Ga and first row transition element contents of olivine grains from suite of PMG and PES by LA-ICP-MS at JSC. Included in the PMG suite are some that have anomalous metal compositions (PMG-am) and atypically ferroan olivines (PMG-as). Our EMPA work has shown that there are unanticipated variations in olivine Fe/Mn, even within those PMG that have uni-form Fe/Mg. Manganese is homologous with Fe2+, and thus can be used the same way to investigate magmatic fractionation processes. It has an advantage for pallasite studies in that it is unaffected by redox exchange with the metal. PMG can be divided into three clusters on the basis of Mn/Mg; low, medium and high that can be thought of as less, typically and more fractionated in an igneous sense. The majority of PMG have medium Mn/Mg ratios. PMG-am occur in all three clusters; there does not seem to be any relationship between putative olivine igneous fractionation and metal composition. The PMG-as and one PMG-am make up the high Mn/Mg cluster; no PMG are in this cluster. The high Mn/Mg cluster ought to be the most fractionated (equivalent to the most Fe-rich in igneous suites), yet they have among the lowest contents of incompatible lithophile elements Al and Ti and the two PMG-as in this cluster also have low Ca and Sc contents. This is inconsistent with simple igneous

  2. Implications for the evolution of chondrules from Agglomeratic olivine chondrules

    NASA Technical Reports Server (NTRS)

    Weisberg, M. K.; Prinz, M.

    1994-01-01

    There is considerable evidence that chondrules formed by the melting of solid materials and, by default, the early solar nebula is the preferred location for chondrule formation. Agglomeratic olivine (AO) chondrules supply perhaps the most intriguing, direct evidence for chondrule formation from agglomeration of solids. We review the characteristics of AO chondrules and discuss their implications for understanding chondrule precursors and chondrule evolution.

  3. Micromechanical modeling of the viscoplastic behavior of olivine

    NASA Astrophysics Data System (ADS)

    Castelnau, O.; Blackman, D. K.; Lebensohn, R. A.; Ponte CastañEda, P.

    2008-09-01

    Efforts to couple mantle flow models with rheological theories of mineral deformation typically ignore the effect of texture development on flow evolution. The fact that there are only three easy slip systems for dislocation glide in olivine crystals leads to strong mechanical interactions between the grains as the deformation proceeds, and subsequent development of large viscoplastic anisotropy in polycrystals exhibiting pronounced Lattice Preferred Orientations. Using full-field simulations for creep in dry polycrystalline olivine at high temperature and low pressure, it is shown that very large stress and strain rate intragranular heterogeneities can build up with deformation, which increase dramatically with the strength of the hard slip system (included for the purpose of enabling general deformations). Compared with earlier nonlinear extensions of the Self-Consistent mean-field theory to simulate polycrystal deformation, the "Second-Order" method is the only one capable of accurately describing the effect of intraphase stress heterogeneities on the macroscopic flow stress, as well as on the local stress- and strain rate fluctuations in the material. In particular, this approach correctly predicts that olivine polycrystals can deform with only four independent slip systems. The resistance of the fourth system (or accommodation mechanism), which is likely provided by dislocation climb or grain boundary processes as has been observed experimentally, may essentially determine the flow stress of olivine polycrystals. We further show that the "tangent" model, which had been used extensively in prior geophysical studies of the mantle, departs significantly from the full-field reference solutions.

  4. Near-Infrared Optical Constants of Olivine and Pyroxene

    NASA Astrophysics Data System (ADS)

    Trang, D.; Lucey, P. G.; Gillis-Davis, J.; Cahill, J. T.; Klima, R. L.; Isaacson, P.

    2012-12-01

    Producing mineral maps of planetary bodies is useful for petrological studies, future colonization, and resources. Estimating the physical and chemical properties of a surface, however, is complicated due to parameters such as, grain size and shape, mineral chemistry, space weathering, and ambient temperature. Radiative transfer modeling is one method to calculate mineral proportions and chemistry from reflectance spectra. However, radiative transfer modeling requires knowledge of the optical constants of minerals of interest. In this study, we characterized the near-infrared optical constants of two common mafic minerals, olivine and pyroxene, with a wide distribution of chemistries. Particularly, we parameterized the imaginary index of refraction, k, in the near-infrared portion of the spectrum of natural olivines as a function of foresterite content and synthetic pyroxenes as a function of wollastonite and ferrosilite content. For each k-spectrum, we modeled each absorption features and continuum using the Modified Gaussian Model (MGM) with three Gaussians and an inverse linear function respectively. We find that our fitting routine characterizes the k-spectra of olivine and pyroxene consistently. Additionally, we described each parameter of MGM and the continuum with a regression or multiple regressions as a function of mineral chemistry. Thus providing the optical parameters of olivine and pyroxene needed for radiative transfer modeling. Scatter observed between optical parameters and mineral chemistry could be the result of minor cations (e.g., Mn2+), grain size, and cation ordering. Future work will seek to characterize these effects on derived optical parameters.

  5. 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.

  6. A Study of Olivine Alteration to Iddingsite Using Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Kuebler, K. E.; Wang, Alian; Haskin, L. A.; Jolliff, B. L.

    2003-01-01

    A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.

  7. 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.

  8. Deformation of olivine in torsion under hydrous conditions

    NASA Astrophysics Data System (ADS)

    Demouchy, Sylvie; Tommasi, Andréa; Barou, Fabrice; Mainprice, David; Cordier, Patrick

    2012-08-01

    We performed torsional deformation experiments on pre-hydrated fine-grained olivine aggregates using an innovative experimental assembly to investigate water weakening in mantle rocks at high shear strains. San Carlos olivine powder was cold-pressed and then hot-pressed under hydrous conditions, producing aggregates with average grain sizes of 7 or 15 μm. Deformation experiments were performed in a high-resolution gas-medium apparatus equipped with a torsional actuator, under a confining pressure of 300 MPa, a temperature of 1200 °C, and constant shear strain rates ranging from 8 × 10-5 to 1.4 × 10-4 s-1. Maximum shear stresses range from 150 to 195 MPa. These values are 30% lower relative to those determined in previous torsion experiments on dry, fined-grained dunites under similar conditions. Textures and microstructures of the starting and deformed specimens were characterized by scanning and transmission electron microscopy. All deformed aggregates exhibit a shape-preferred orientation marking a foliation and lineation, as well as a reduction in mean grain size from 15 μm down to 3-4 μm due to dynamic recrystallization. Olivine crystallographic fabrics developed rapidly (γ < 0.1), but their strength, characterized by the J-index, is low compared to naturally deformed peridotites or to polycrystalline olivine deformed at similar finite shear strains under dry conditions. The crystallographic fabrics are consistent with deformation by a dislocation accommodated creep mechanism with activation of multiple {0 k l}[1 0 0] systems, among which the (0 1 0)[1 0 0] slip system is dominant, and minor participation of the (0 1 0)[0 0 1] slip system. Transmission electron microscopy confirmed the occurrence of dislocations with [1 0 0] and [0 0 1] Burgers vectors in most grains. Analysis of unpolarized infrared spectra indicates that hydrogen concentration in the olivine lattice is below the saturation level of 18 ppm wt H2O, which is similar to those typically

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. 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

  14. 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

  15. 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.%.

  16. 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.

  17. 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.

  18. 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.

  19. Diffusion of REE, Hf and Sr in Olivine

    NASA Astrophysics Data System (ADS)

    Remmert, P.; Dohmen, R.; Chakraborty, S.

    2008-12-01

    We have determined diffusion coefficients of the rare earth elements Ce, Nd, Sm, Eu, Lu, and also of Sr and Hf, in single crystals of natural olivine at atmospheric pressure, at an oxygen fugacity of 10-5 Pa and a temperature of 1275 °C. Sources of diffusants were thin films of olivine composition doped with the relevant elements. Thin films were produced by PLD (pulsed laser deposition) and RBS (Rutherford backscattering) was used to measure thickness and stoichiometry of the films as well as to analyze the concentration profiles. The concentration profiles were numerically fitted to yield the following diffusion coefficients (D, in m2/s): log DCe: -19.61 ± 0.21; log DNd: -19.54 ± 0.11; log DSm: -19.15 ± 0.05; log DEu: -19.10; log DLu: -19.00, log DHf: -20.23 ± 0.07; log DSr: -18.7. Diffusion coefficients of the rare-earth elements increase from Ce to Lu, demonstrating the role of ionic radius in controlling diffusion because all REE are trivalent. The tetravalent and divalent cations hafnium and strontium diffuse an order of magnitude slower and faster, respectively, than the REE in olivine. This highlights the important influence of ionic charge on diffusion rates. The diffusion coefficients of the REE are slower by a few orders of magnitudes than the diffusion rate of Cr in olivine [1]. The rates found in this study are slower than those assumed by a model [2] for compositional modification of melt inclusions in olivine. Use of our data in their calculations indicates that it will take longer to modify the composition of melt inclusions in olivine (millions of years rather than thousands of years) but the fractionation of HREE from LREE will be larger. [1] Ganguly J, Ito M (2006) Geochim Cosmochim Acta, 70, 799-809. [2] Cottrell E, Spiegelman M, Langmuir CH (2002) Geochem Geophys Geosyst, doi:10.1029/2001GC000205

  20. 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

  1. 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.

  2. Olivine separates from Murchison and Cold Bokkeveld - Particle tracks and noble gases

    NASA Technical Reports Server (NTRS)

    Macdougall, J. D.; Phinney, D.

    1977-01-01

    Olivine separates from Murchison and Cold Bokkeveld were analyzed for particle tracks and noble gases. The matrix remaining after olivine separation was also analyzed for noble gases. The olivines from both meteorites have comparable fractions of solar-flare-irradiated grains, but the highest track densities in Murchison are an order of magnitude greater than those in Cold Bokkeveld. Solar Ne content in Murchison olivines follows this trend, being at least an order of magnitude higher than that in Cold Bokkeveld. Track gradients in Cold Bokkeveld olivines are flatter than those in Murchison or recently exposed lunar crystals. Relative to the matrix, olivine separates in both meteorites have small enrichments at the heavy and light Xe isotopes and smaller Ar-36/Ar-38 ratios. These noble-gas effects may be related to a chromite impurity in the olivine separates.

  3. 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.

  4. Helium diffusion in olivine based on first principles calculations

    NASA Astrophysics Data System (ADS)

    Wang, Kai; Brodholt, John; Lu, Xiancai

    2015-05-01

    As a key trace element involved in mantle evolution, the transport properties of helium in the mantle are important for understanding the thermal and chemical evolution of the Earth. However, the mobility of helium in the mantle is still unclear due to the scarcity of measured diffusion data from minerals under mantle conditions. In this study, we used first principles calculations based on density functional theory to calculate the absolute diffusion coefficients of the helium in olivine. Using the climbing images nudged elastic band method, we defined the diffusion pathways, the activation energies (Ea), and the prefactors. Our results demonstrate that the diffusion of helium has moderate anisotropy. The directionally dependent diffusion of helium in olivine can be written in Arrhenius form as follows.

  5. 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.

  6. High shear strain of olivine aggregates: rheological and seismic consequences.

    PubMed

    Bystricky, M; Kunze, K; Burlini, L; Burg, J

    2000-11-24

    High-pressure and high-temperature torsion experiments on olivine aggregates in dislocation creep show about 15 to 20% strain weakening before steady-state behavior, characterized by subgrain-rotation recrystallization and a strong lattice preferred orientation. Such weakening may provide a way to focus flow in the upper mantle without a change in deformation mechanism. Flow laws derived from low strain data may not be appropriate for use in modeling high strain regions. In such areas, seismic wave propagation will be anisotropic with an axis of approximate rotational symmetry about the shear direction. In contrast to current thinking, the anisotropy will not indicate the orientation of the shear plane in highly strained, recrystallized olivine-rich rocks. PMID:11090352

  7. 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.

  8. 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.

  9. 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

  10. Creep behavior of Fe-bearing olivine under hydrous conditions

    NASA Astrophysics Data System (ADS)

    Tasaka, Miki; Zimmerman, Mark E.; Kohlstedt, David L.

    2015-09-01

    To understand the effect of iron content on the creep behavior of olivine, (MgxFe(1 - x))2SiO4, under hydrous conditions, we have conducted tri-axial compressive creep experiments on samples of polycrystalline olivine with Mg contents of x = 0.53, 0.77, 0.90, and 1. Samples were deformed at stresses of 25 to 320 MPa, temperatures of 1050° to 1200°C, a confining pressure of 300 MPa, and a water fugacity of 300 MPa using a gas-medium high-pressure apparatus. Under hydrous conditions, our results yield the following expression for strain rate as a function of iron content for 0.53 ≤ x ≤ 0.90 in the dislocation creep regime: ɛ˙=ɛ˙0.90((1-x/0.1))1/2exp[226×1030.9-x/RT]. In this equation, the strain rate of San Carlos olivine, ɛ˙0.90, is a function of T, σ, and fH2O. As previously shown for anhydrous conditions, an increase in iron content directly increases creep rate. In addition, an increase in iron content increases hydrogen solubility and therefore indirectly increases creep rate. This flow law allows us to extrapolate our results to a wide range of mantle conditions, not only for Earth's mantle but also for the mantle of Mars.

  11. Olivine crystals align during diffusion creep of Earth's upper mantle.

    PubMed

    Miyazaki, Tomonori; Sueyoshi, Kenta; Hiraga, Takehiko

    2013-10-17

    The crystallographic preferred orientation (CPO) of olivine produced during dislocation creep is considered to be the primary cause of elastic anisotropy in Earth's upper mantle and is often used to determine the direction of mantle flow. A fundamental question remains, however, as to whether the alignment of olivine crystals is uniquely produced by dislocation creep. Here we report the development of CPO in iron-free olivine (that is, forsterite) during diffusion creep; the intensity and pattern of CPO depend on temperature and the presence of melt, which control the appearance of crystallographic planes on grain boundaries. Grain boundary sliding on these crystallography-controlled boundaries accommodated by diffusion contributes to grain rotation, resulting in a CPO. We show that strong radial anisotropy is anticipated at temperatures corresponding to depths where melting initiates to depths where strongly anisotropic and low seismic velocities are detected. Conversely, weak anisotropy is anticipated at temperatures corresponding to depths where almost isotropic mantle is found. We propose diffusion creep to be the primary means of mantle flow. PMID:24132289

  12. The effect of water on the electrical conductivity of olivine.

    PubMed

    Wang, Duojun; Mookherjee, Mainak; Xu, Yousheng; Karato, Shun-ichiro

    2006-10-26

    It is well known that water (as a source of hydrogen) affects the physical and chemical properties of minerals--for example, plastic deformation and melting temperature--and accordingly plays an important role in the dynamics and geochemical evolution of the Earth. Estimating the water content of the Earth's mantle by direct sampling provides only a limited data set from shallow regions (<200 km depth). Geophysical observations such as electrical conductivity are considered to be sensitive to water content, but there has been no experimental study to determine the effect of water on the electrical conductivity of olivine, the most abundant mineral in the Earth's mantle. Here we report a laboratory study of the dependence of the electrical conductivity of olivine aggregates on water content at high temperature and pressure. The electrical conductivity of synthetic polycrystalline olivine was determined from a.c. impedance measurements at a pressure of 4 GPa for a temperature range of 873-1,273 K for water contents of 0.01-0.08 wt%. The results show that the electrical conductivity is strongly dependent on water content but depends only modestly on temperature. The water content dependence of conductivity is best explained by a model in which electrical conduction is due to the motion of free protons. A comparison of the laboratory data with geophysical observations suggests that the typical oceanic asthenosphere contains approximately 10(-2) wt% water, whereas the water content in the continental upper mantle is less than approximately 10(-3) wt%. PMID:17066032

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. Phosphorus zoning in olivine of Kilauea Iki lava lake, Hawaii

    NASA Astrophysics Data System (ADS)

    Fabbrizio, Alessandro; Beckett, John R.; Baker, Michael B.; Stolper, Edward M.

    2010-05-01

    Kilauea Iki lava lake was formed when the lavas of the 1959 summit eruption of Kilauea volcano ponded in Kilauea Iki pit crater, as described by [1]. The main chamber of this lake has been drilled repeatedly from 1960 to 1981 as the lake has cooled and crystallized and partial descriptions of core can be found in [2-7]. The bulk of the core consists of a gray, olivine-phyric basalt matrix [3]. Rapid diffusion of divalent cations through olivine at magmatic temperatures can delete information on early-formed zoning and thus information on early magmatic history, recorded in olivine during its growth, is often largely lost [8-11]. In the last years many studies [8-11] have shown that natural olivine, terrestrial and extraterrestrial, from several localities and rock types can preserve a complex zoning in P (sometimes associated with Cr and Al). Simple crystallization experiments conducted by [10] and [11] were able to replicate these features (i.e., sector and oscillatory zoning). Here, we describe P, Cr and Al zoning in olivine from the 1981 drilling of Kilauea Iki lava lake hole #1 (KI81-1) [6]. Kα X-ray intensity maps and major and minor element quantitative analyses were obtained using the Caltech JEOL JXA-8200 electron microprobe. We acquired P, Cr, Al, Fe and Ti X-ray maps simultaneously at 15 kV and 400 nA, a beam diameter of 1 μm, pixel spacing of 1-2 μm, and count times of 420-1500 msec/step were used depending on the dimension of the crystal. 15 kV and 40 nA with a beam diameter of 1 μm were used to collect quantitative analyses. P2O5 contents of the Iki olivines range from below detection limit to 0.30 wt%. Zoning in phosphorus, based on X-ray intensity maps, was observed in all olivines we examined. The P zoning patterns of the olivines display several styles. P shows oscillatory zoning comparable to that seen in terrestrial and extraterrestrial igneous olivines and in experimentally grown olivine [8-11]; high P regions, inside the crystals, outline

  19. 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

  20. Producing Ni-rich olivine phenocrysts by mixing partial melts of eclogite and peridotite: an alternative to an olivine-free source for Hawaiian shield basalts

    NASA Astrophysics Data System (ADS)

    Wang, Z.; Gaetani, G.

    2007-12-01

    It has been posited that presence of unusually Ni-rich (2500-4000 ppm) magnesian olivine phenocrysts in SiO2-enriched Hawaiian shield-building basalts, most notably the Koolau lavas, is inconsistent with a deep, olivine-bearing source rock. Instead, Sobolev et al. (2005) proposed that these lavas are generated by a multi- stage process in which partial melts of eclogite react with peridotite within the plume to form an olivine-free source rock with high Ni concentration. As the plume continues to ascend, partial melts of this "hybrid" pyroxenite mix with peridotite melts to produce SiO2- enriched Hawaiian shield-building lavas that crystallize high-Ni olivine. This model has also been used to argue for significant amounts of "hybrid" pyroxenite in the source regions of lavas from other ocean islands, continental basalts, and even MORB, implying that the upper mantle is highly heterogeneous (Sobolev et al., 2007). New experimental results demonstrate that Ni-rich magnesian olivine crystallizes from mixtures of peridotite partial melt and Ni-poor eclogite partial melt that have equilibrated with mantle olivine. This occurs because the concentration of Ni decreases linearly as eclogite partial melt is added to peridotite partial melt, whereas changing major element composition of the mixed melts causes DNi to increase hyperbolically. Experiments were conducted in which either (1) siliceous partial melt of eclogite or (2) primitive basalt was equilibrated with San Carlos olivines at 1 bar and 1201-1350°C. Experimental results demonstrate that eclogite partial melts in equilibrium with mantle olivine retain their high SiO2, low FeO and MgO characteristics. Theoretical modeling calibrated from these experimental results suggest that reaction of siliceous eclogite melt with mantle olivine at low pressure produces a melt containing ~300 ppm Ni. Despite its low Ni content, mixing of this melt with peridotite partial melt produces a high SiO2 melt that crystallizes Ni

  1. 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

  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. PMID:24369634

  3. 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.

  4. Petrogenetic linkages among Martian basalts: Implications based on trace element chemistry of olivine

    NASA Astrophysics Data System (ADS)

    Shearer, C. K.; Burger, P. V.; Papike, J. J.; Borg, L. E.; Irving, A. J.; Herd, C.

    2008-10-01

    The shergottites exhibit a range of major and trace element compositions, crystallization ages, and initial Sr, Nd, Hf, and Pb isotopic compositions. To constrain the physical mechanisms by which shergottites obtain their compositional characteristics, we examined the major and trace element record preserved in olivine in the more primitive shergottites. Based on such characteristics as the Mg#, V zoning, calculated DNi,Co, the olivine in Y-980459 are most likely phenocrysts. Many of these same characteristics indicate that the olivines in other shergottites are not in equilibrium with the adjacent melt. However, in most cases they are not xenocrystic, but additions of olivine from the same basaltic system. Elephant Moraine (EET) A79001 may be an exception with the olivine data suggesting that it is xenocrystic. In this case, the olivine crystallized from a reduced and LREEdepleted melt and was incorporated into an oxidized and enriched basalt. Vanadium and CaO in olivine appear to record the appearance of spinel and pyroxene on the liquidus of most of the shergottites. Most of the olivine shergottites represent basalts produced by melting of reduced (IW to IW + 1), depleted mantle sources. Olivine data indicate that many of the primary melts derived from this source had similar Ni, Co, and Mn. Shergottites such as Northwest Africa (NWA) 1110/1068 and perhaps Roberts Massif (RBT) 04261 that appear to be derived from more enriched sources have distinctly different olivine. In the case of NWA 1110/1068, the olivine data suggests that the enriched component was added to system prior to olivine crystallization.

  5. 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.

  6. 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.

  7. 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

  8. Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe

    NASA Astrophysics Data System (ADS)

    Koch-Müller, Monika; Matsyuk, Stanislav S.; Rhede, Dieter; Wirth, Richard; Khisina, Natasha

    2006-06-01

    The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to -180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730 3,330 cm-1. Bands at high energies (3,730 3,670 cm-1) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm-1 E || a, 3,597 E || a, 3,571 cm-1 E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2 H groups may be responsible for the OH bands at higher wavenumbers than those for the O1 H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H2O cm-2 is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105 2113, 2003) (28,450±1,830 L mol H2O cm-2). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm-1). Olivine samples with a mean wavenumber of about 3

  9. Argon Diffusion in Shocked Pyroxene, Feldspar, and Olivine

    NASA Astrophysics Data System (ADS)

    Weirich, J.; Isachsen, C. E.; Johnson, J. R.; Swindle, T.

    2010-12-01

    Background: The diffusion rate of argon (Ar) in unshocked feldspar has been well studied, but studies on pyroxene and olivine are limited or non-existent. Likewise, the effects of shock on these mineral groups is also limited or non-existent. Understanding how shock affects these mineral groups is important for determining the thermal history of shocked meteorites and collisional impact craters. We have analyzed the Ar diffusion rate of an albitite and a pyroxenite at various experimental shock pressures up to ~60GPa, unshocked high-Ca pyroxene, and an olivine mineral separate from the Springwater meteorite. A previous study of shocked feldspar has shown that Ar diffusion in plagioclase (An67) is unaffected by experimental shock [1]. Re-reduction of data from another study [2] suggests naturally shocked K-rich feldspar is affected, though experimentally shocked oligoclase feldspar (An10-30) is not affected. However, previous shock experiments on feldspar were performed with low temperature resolution and only a single extraction at each temperature. This makes determining the diffusion parameters difficult because the presence of multiple grain sizes can compromise the data. By performing our experiments with a higher temperature resolution and with two extractions at each temperature, we can attain higher quality and more reliable data. The effects of shock on pyroxene and olivine have never been studied. Results: We have found that experimental shock undoubtedly raises the diffusivity of albite (Ab97), and lowers the activation energy required for diffusion. Comparison with previous data indicates that the Ca content may be controlling the response to shock. Pyroxene seems to be somewhat variable regardless of shock pressure, even within the same sample. Shock may have an effect on the diffusion rate of pyroxene, but given the variability it is difficult to delineate. The range of pyroxene diffusion rates is similar to previous studies. Olivine is found to have a

  10. Inherited Pb isotopic records in olivine antecryst-hosted melt inclusions from Hawaiian lavas

    NASA Astrophysics Data System (ADS)

    Sakyi, Patrick Asamoah; Tanaka, Ryoji; Kobayashi, Katsura; Nakamura, Eizo

    2012-10-01

    Dislocation textures of olivine grains and Pb isotopic compositions (207Pb/206Pb and 208Pb/206Pb) of olivine-hosted melt inclusions in basaltic lavas from three Hawaiian volcanoes (Kilauea, Mauna Loa, and Koolau) were examined. More than 70% of the blocky olivine grains in the studied samples have a regular-shaped dislocation texture with their dislocation densities exceeding 106 cm-2, and can be considered as deformed olivine. The size distribution of blocky olivine grains shows that more than 99% of blocky olivines coarser than 1.2 mm are identified as deformed olivine. These deformed olivine grains are identified as antecrysts, which originally crystallized from previous stages of magmatism in the same shield, followed by plastic deformation prior to entrainment in the erupted host magmas. This study revealed that entrainment of mantle-derived crystallization products by younger batches of magma is an important part of the evolution of magnesium-rich Hawaiian magma. Lead isotopic compositions of melt inclusions hosted in the olivine antecrysts provide information of the evolutionary history of Hawaiian volcanoes which could not have been accessed if only whole rock analyses were carried out. Antecryst-hosted melt inclusions in Kilauea and Koolau lavas demonstrate that the source components in the melting region changed during shield formation. In particular, evidence of interaction of plume-derived melts and upper mantle was observed in the earliest stage of Koolau magmatism.

  11. Mantle Origin of Olivine-rich Troctolites in a Rift Environment

    NASA Astrophysics Data System (ADS)

    Faul, U.; Garapic, G.; Michibayashi, K.

    2014-12-01

    Olivine-rich troctolites from Krivaja-Konjuh massif in the Dinarides (Bosnia and Herzegovina) represent a unique natural laboratory to study melt segregation and retention in originally fertile rift-related mantle rocks. Petrographic and chemical analyses of coexisting minerals (olivine and interstitial clinopyroxene, spinel and plagioclase) show that olivine and spinel are of mantle origin, and interstitial clinopyroxene and plagioclase are products of crystallization of trapped melt. Geochemical and microstructural observations (dissolution of pyroxene) indicate that this trapped melt started off at larger depth and that it was silica undersaturated when it reached the plagioclase stability field. The original mantle olivine remained and texturally equilibrated with the melt, which is evident from the high Ni content and euhedral crystal habit in thin sections. This suggests that the melt that crystallized the interstitial phases, clinopyroxene and plagioclase, was saturated in olivine and probably similar to MORB-type melt. The interstitial phases show no sign of deformation. A mantle origin of olivine is corroborated by EBSD data that show a progressive misorientation across individual olivine grains due to previous episodes of deformation within the mantle. By contrast, grains originating from cumulate crystallization should show little internal deformation. Therefore we suggest that olivine-rich troctolites are not crystallization products, but rather products of reaction of melt with the lherzolitic mantle. The evidence of trapped melt in those rocks provides a new insight into the crust-mantle transition at slow spreading ridges and continental rifts where olivine-rich troctolites have been observed.

  12. Lamellar olivine in the Divnoe achondrite: Evidence for high-pressure exsolution?

    NASA Technical Reports Server (NTRS)

    Petaev, M. I.

    1993-01-01

    The olivine-rich Divnoe achondrite contains numerous large olivine grains which have a lamellar or banded appearance in back-scattered electron images, caused by minor compositional differences. One such grain, viewed in transmitted light, displays a system of lamellae with the same orientation and scale as the compositional banding. The only process known to produce such structure and chemical variability in olivine grains is high-pressure transformations between alpha-, beta- and gamma-olivines, but in other meteorites and in experimental products the structure is approximately 100 times finer than the Divnoe lamella.

  13. 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

  14. 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.

  15. Low-temperature plastic rheology of olivine determined by nanoindentation

    NASA Astrophysics Data System (ADS)

    Kranjc, Kelly; Rouse, Zachary; Flores, Katharine M.; Skemer, Philip

    2016-01-01

    Low-temperature plasticity is a deformation mechanism that occurs mainly at high stress and low temperatures and may be important in the shallow lithosphere, at the tips of cracks, and in laboratory experiments. Previous studies investigating the low-temperature plasticity of the mineral olivine have exhibited wide variability in their extrapolations to the athermal flow strength or Peierls stress. To better constrain the rheology of olivine, nanoindentation tests were performed on samples in the temperature range of 0-175°C. The indentation properties were converted to uniaxial properties using a finite element-based method. The data were fit to a standard flow law for low-temperature plasticity, and Peierls stresses between 5.32 and 6.45 GPa were obtained. These results provide increased confidence in the extrapolation of high-pressure and high-temperature laboratory experiments to low-temperature conditions and illustrate the applicability of nanoindentation methods to the study of mineral rheology.

  16. B-type olivine fabric induced by grain boundary sliding

    NASA Astrophysics Data System (ADS)

    Précigout, Jacques; Hirth, Greg

    2014-06-01

    Mineral Lattice Preferred Orientation (LPO) in naturally deformed peridotite is typically interpreted to result from the motion of intra-crystalline dislocations during dislocation creep. The degree of mineral alignment (fabric strength) is often assumed to increase with increasing finite strain. Here, we document olivine LPOs in peridotites in a kilometer-scale mantle shear zone in the Ronda massif (Spain) that demonstrate a transition from a flow-parallel [100]-axis LPO (A-type fabric) to a flow-normal [100]-axis LPO (B-type fabric). We conclude that the B-type fabric in the Ronda peridotite results from the enhancement of grain boundary sliding (GBS) with decreasing grain size, rather than a change in the dominant dislocation slip system because: (1) dislocation sub-structures remain consistent with the A-type slip system in all samples; (2) the fabric transition correlates with decreasing fabric strength despite increasing finite strain; (3) the analysis of deformation conditions in Ronda is inconsistent with the experimental conditions, including water content, inferred to promote the dominance of (010)[001] slip in laboratory samples, and (4) our observations are supported by experiments that document B-type fabric in olivine aggregates where deformation involves a component of GBS. Our results have important implications for interpreting the rheological properties of shear zones and upper mantle structures via micro-structural and seismic observations.

  17. 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.

  18. Temperature-dependent Infrared Optical Constants of Olivine and Enstatite

    NASA Astrophysics Data System (ADS)

    Zeidler, S.; Mutschke, H.; Posch, Th.

    2015-01-01

    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.

  19. Type-C olivine LPOs in garnet peridotites in North Qaidam UHP collision belt, NW China

    NASA Astrophysics Data System (ADS)

    Jung, H.; Lee, J.; Ko, B.; Jung, S.; Park, M.; Cao, Y.; Song, S.

    2013-12-01

    Water is known to change the lattice-preferred orientation (LPO) of olivine, which significantly affects seismic anisotropy in the Earth's upper mantle. Research into the LPO of olivine in the deep interior of the Earth has been limited due to inadequate specimens. We report both the water-induced LPOs of olivine and the presence of large quantities of water inside olivine, enstatite, and garnet in garnet peridotites from the North Qaidam ultrahigh-pressure (UHP) collision belt in NW China. We show that the [001] axis of olivine is aligned subparallel to the lineation and that the [100] axis is strongly aligned subnormal to the foliation. This alignment is a known feature of type-C LPO of olivine formed experimentally under water-rich conditions (≥700 ppm H/Si) at high pressure and temperature. Enstatite possessed an LPO with the [001] axis aligned parallel to the lineation and the [100] axis aligned normal to the foliation. FTIR analysis of this specimen revealed that olivine contained concentrations of water up to 1130 × 50 ppm H/Si in clean areas, whereas olivine, enstatite, and garnet contained considerably more water, i.e., 2600 × 100 ppm H/Si, 5000 × 100 ppm H/Si, and 21000 × 200 ppm H/Si, respectively, when exsolved inclusions were visible. Confocal micro-Raman spectroscopy of these exsolved inclusions revealed that they were composed of hornblende and amphiboles. Straight dislocations were also commonly observed in olivine and are characteristic of olivine that had been experimentally deformed under hydrous conditions. These observations suggest that the type-C LPO of olivine in the North Qaidam UHP belt formed under water-rich conditions.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

    Treiman, A. H.

    2005-03-01

    Low-temperature carbonate globules in ALH84001 are found near olivine grains that equilibrated at T>800° C. Terrestrial analogs from Spitsbergen (Norway) suggest an explanation of this association; the carbonate globules may have been deposited in cavities where olivine had been dissolved out.

  2. 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.

  3. Experimental modeling of the cooling history of Apollo 12 olivine basalts

    NASA Technical Reports Server (NTRS)

    Donaldson, C. H.; Usselman, T. M.; Williams, R. J.; Lofgren, G. E.

    1975-01-01

    An analog of the Apollo 12 olivine vitrophyres has been crystallized in a 1-atm gas-mixing furnace at cooling rates ranging between 1250 and 0.7 C/hr and isothermally at degrees of supercooling ranging from 10 C to 325 C. Mineral chemistry, crystal shapes, grain sizes and textures are systematically related to cooling rate and degree of supercooling. At linear cooling rates not exceeding 40 C/hr the texture is porphyritic - large olivine crystals are set in a groundmass of finer-grained pyroxene, plagioclase, and ilmenite; a later generation of olivine never crystallizes. There are three shapes of olivine crystals in the Apollo 12 olivine vitrophyres: glomerocrysts of subhedral crystals, large subequant skeletons, and highly elongate skeletons. These result from three generations of nucleation and a two-stage cooling history - a slow preeruption stage and a rapid continuously increasing posteruption stage. It seems likely that the Apollo 12 olivine basalt magmas were erupted with olivine crystals in suspension. The nucleation temperature of olivine in cooling-rate experiments is dependent on the experimental technique, and hence results of cooling experiments should be applied with caution.

  4. Hydrous olivine unable to account for conductivity anomaly at the top of the asthenosphere.

    PubMed

    Yoshino, Takashi; Matsuzaki, Takuya; Yamashita, Shigeru; Katsura, Tomoo

    2006-10-26

    The oceanic asthenosphere is observed to have high electrical conductivity, which is highly anisotropic in some locations. In the directions parallel and normal to the plate motion, the conductivity is of the order of 10(-1) and 10(-2) S m(-1), respectively, which cannot be explained by the conductivity of anhydrous olivine. But because hydrogen can be incorporated in olivine at mantle pressures, this observation has been attributed to olivine hydration, which might cause anisotropically high conductivity by proton migration. To examine this hypothesis, here we report the effect of water on electrical conductivity and its anisotropy for hydrogen-doped and undoped olivine at 500-1,500 K and 3 GPa. The hydrous olivine has much higher conductivity and lower activation energy than anhydrous olivine in the investigated temperature range. Nevertheless, extrapolation of the experimental results suggests that conductivity of hydrous olivine at the top of the asthenosphere should be nearly isotropic and only of the order of 10(-2) S m(-1). Our data indicate that the hydration of olivine cannot account for the geophysical observations, which instead may be explained by the presence of partial melt elongated in the direction of plate motion. PMID:17066031

  5. 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.

  6. Solubility of TiO2 in Olivine from 1 to 8 Gpa

    NASA Astrophysics Data System (ADS)

    Tinker, D.; Lesher, C. E.

    2001-12-01

    Laboratory experiments have been conducted to determine the solubility of TiO2 in olivine from 1 to 8 GPa, between 1127° and 1560° C. These experiments were performed in the piston cylinder device (1 and 2 GPa) and the MA6/MA8 multianvil apparatus (3 to 8 GPa), using starting materials consisting of San Carlos olivine and 20 wt % TiO2 powder. Excess TiO2 forms rutile in all run products. The presence of rutile imposes unit activity of TiO2 in olivine and, thus, we measure maximum solubilities of Ti in olivine. This situation differs from studies in which olivine is in equilibrium with ilmenite [1,2,3]. Electron microprobe analyses of run products show that the TiO2 content of olivine has positive pressure dependence between 1 and 8 GPa. Olivine contains 0.2 wt % TiO2 between 1 and 3 GPa, at 1127° and 1460° C; TiO2 contents increase to 0.5 wt % between 3 and 8 GPa. Dobrzhinetskaya et al. [1] and Green et al. [2] observed a similar positive pressure dependence on TiO2 solubility in olivine between 6 and 14 GPa. However, TiO2 contents of olivine from 6 to 8 GPa in these studies are lower than TiO2 contents we find between 6 and 8 GPa. Lower TiO2 contents presumably reflect ilmenite-olivine equilibria. In contrast, Okamoto et al. [3] and Ulmer and Trommsdorff [4] did not report a positive pressure dependence on TiO2 solubility in olivine, although rutile was stable in the experiments of [4]. The positive pressure dependence of TiO2 solubility is important for the interpretation of high pressure metamorphic rocks containing abundant exsolved titanate rods, which on recombination can yield 0.6 wt % TiO2 in host olivine before exsolution [5]. We estimate from our data that olivine containing 0.6 wt % TiO2 originated at a minimum depth of 10 GPa. The positive pressure dependence of TiO2 in olivine offers an additional pathway for the transport of Ti and other high field strength elements into the mantle, and these elements may later be recovered by rising mantle plumes

  7. 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.

  8. The Mn-Fe negative correlation in olivines in ALHA 77257 ureilite

    NASA Astrophysics Data System (ADS)

    Miyamoto, M.; Furuta, T.; Fujii, N.; McKay, D. S.; Lofgren, G. E.; Duke, M. B.

    1993-03-01

    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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Phyllosilicate and Olivine around a Fracture in Nili Fossae

    NASA Technical Reports Server (NTRS)

    2007-01-01

    iron- and magnesium-rich mineral olivine. Olivine and pyroxene are minerals associated with igneous activity.

    Overlaying CRISM data with images from the High-Resolution Imaging Science Experiment (HiRISE) camera shows that the phyllosilicates are in small, eroded outcrops of rock. The olivine is most abundant in sand dunes on the surface. The use of these two instruments together reveals more about the history of the region: Olivine sands covered the area shown in the image after the interaction of water and rock formed the phyllosilicates and after the fracture formed.

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad.

  14. Olivine-type NaCd(AsO4)

    PubMed Central

    Weil, Matthias

    2013-01-01

    The title compound, sodium cadmium orthoarsenate, adopts the olivine [Mg2(SiO4)] structure type in space group Pnma, with Na (site symmetry -1) and Cd (.m.) replacing the two Mg positions, and the AsO4 tetra­hedron (.m.) the SiO4 tetra­hedron. The crystal structure is made up of a nearly hexa­gonal closed-packed arrangement of O atoms stacked along [001]. The Na and Cd atoms occupy one half of the octa­hedral voids in alternate layers stacked along [100], and one eighth of the tetra­hedral voids are occupied by As atoms. PMID:24454011

  15. Olivines in angrite LEW 87051: Phenos or xenos

    NASA Technical Reports Server (NTRS)

    Mckay, G.; Le, L.; Wagstaff, J.

    1991-01-01

    Nyquist et al. recently reported the presence of live Mn-53 in angrite LEW 86010 when it crystallized. Hence, melting must have occurred within approx. 10 Ma of the accretion of the angrite parent body, and LEW 86010 is the oldest known differentiated meteorite. This discovery has made it even more desirable to understand teh petrogenesis of angrites, which presumably were all formed at a similar time. As part of the continuing work on angrite petrogenesis, crystallization experiments were conducted on LEW 87051, the other Antarctic angrite, to clarify its petrogenesis. Several aspects of the experimental work is reported. Although the details are not understood, it is clear that the Cr abundance in the experimental olivines must be controlled by spinel crystallization.

  16. 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.

  17. Stereochemically constrained complex organic molecules extracted from olivine crystal matrix

    NASA Astrophysics Data System (ADS)

    Gerasimenko, I.; Freund, F. T.; Imanaka, H.; Rodgers, R.

    2011-12-01

    Paradoxically, the dense solid state of magmatic minerals is a medium, in which organic synthesis can take place. The reason is that gas-fluid components such as H2O, CO/CO2/N2 and H2S are omnipresent in terrestrial magmatic environments. Any silicate mineral that crystallizes from such magmas will incorporate small quantities of the fluid-phase components in the form of structurally incompatible low-z impurities. During cooling the solute species undergo a redox conversion, resulting in chemically reduced low-z elements. To the extent that these low-z impurities are diffusively mobile, they will exsolve to the surface and/or to major structural defects inside the crystal matrix such as dislocations. Dislocations provide a 3-D structured environment, where the low-z impurities will tend to form stereochemically constrained polyatomic Cn-H-O-N-S entities, which we call organic protomolecules. In Nature, during weathering, such protomolecules will be released into the environment in the form of complex organic molecules. In our study we crush samples under clean conditions as a way to expose Cn-H-O-N-S entities at the fracture surfaces. We conduct identical experiments with selected large olivine single crystals, mm-sized olivine from peridiotite nodules from the San Carlos Volcanic Field, Arizona, and the vesiculated basalt that had carried the nodules upward in the volcanic conduit. We Soxhlet-extract the crushed powders with water, THF and ethyl acetate. The extracts are analyzed at the FTICR-MS facility at Florida State University using ultrahigh resolution Mass Spectrometry techniques capable of determining the chemical composition of the organic molecules up to 600 amu and more. So far we have found several analog sequences of oxygen-rich aliphatic hydrocarbons, families with up to 34 carbon atoms, probably poly-carboxylic acids, and some families containing sulfur.

  18. 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.

  19. 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.

  20. 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

  1. Hydrogen in the upper mantle: Diffusion and effects on olivine transformation kinetics

    NASA Astrophysics Data System (ADS)

    Du Frane, Wyatt Louis

    Olivine is the most abundant mineral in Earth's upper mantle and can host significant amounts of hydrogen within its crystal structure. The presence of hydrogen affects many of olivine's physical properties such as electrical conductivity, viscosity, sound speed, transformation kinetics, phase equilibrium, and generally speaking the physics governing the interior of the earth. Understanding how hydrogen affects olivine is integral to understanding the Earth's interior. In this work olivine was experimentally hydrated and reacted at high pressure and temperature, to simulate upper mantle conditions. The physical properties measured in this work are used to understand seismic and magnetotelluric observations of the Earth. In the first project the effects of hydrogen on olivine transformation kinetics were examined. Growth rates for olivine's high pressure polymorphs, wadsleyite and ringwoodite, to determine if olivine can persist metastably inside cold subducting slabs in the mantle transition zone. Hydrogen significantly enhances the growth rates of olivine into ringwoodite. For olivine containing ˜75 (or higher) ppmw H2O At 18 GPa and 900°C the growth rate for ringwoodite rims is 1.0x10-9 m/s with activation enthalpy of 235 +/- 30 kJ/mol, which is too high for persistence of metastable olivine into the transition zone. Confirmation of the existence of metastable olivine by seismologists would constrain H2O contents at such locations to be < 75 ppmw H2O. In the second project deuterium-hydrogen interdiffusion coefficients were measured to help understand electrical conductivity, point defect populations, chemical transport, and defect dominated properties in olivine. For the fastest H-diffusing [100] orientation DD-H, [100] = 10(-5.04 +/- 1.43)*e(-137 +/- 31 kJ/mol)/(RT) m²/s at 2 GPa and 750--900°C. Comparison of DD-H to chemical diffusion coefficients allows us to calculate diffusivity of intrinsic defects. Olivine electrical conductivity is calculated from DD

  2. 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

  3. Martian Dunite NWA 2737: Petrographic constraints on geological history, shock events, and olivine color

    NASA Astrophysics Data System (ADS)

    Treiman, Allan H.; Dyar, M. Darby; McCanta, Molly; Noble, Sarah K.; Pieters, Carle M.

    2007-04-01

    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, Mössbauer spectra, and synchrotron micro-XANES spectroscopy) and with ~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 ~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 {021} planes: These are consistent with the easy slip law for olivine [100]{021}, which is activated at moderate strain rate at high temperature. Within these

  4. 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.

  5. 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.

  6. The influence of water on the Peierls stress of olivine at high pressures

    NASA Astrophysics Data System (ADS)

    Mei, S.; Suzuki, A. M.; Xu, L.; Kohlstedt, D. L.; Dixon, N. A.; Durham, W. B.

    2012-04-01

    To investigate the influence of water on the low-temperature plasticity of olivine under lithospheric conditions, we carried out a series of creep experiments on polycrystalline olivine at high pressures (~6 GPa), relatively low temperatures (873 ≤ T ≤ 1173 K), and hydrous conditions using a deformation-DIA. Samples were fabricated from fine powdered San Carlos olivine under hydrous conditions. In the experiments, a sample column composed of a sample and alumina pistons was assembled with a talc sleeve and graphite resistance heater into a 6.2-mm edge length cubic pressure medium. Experiments were carried out at the National Synchrotron Light Source at Brookhaven National Laboratory. In a run, differential stress and sample displacement were monitored in-situ using synchrotron x-ray diffraction and radiography, respectively. The low-temperature plasticity of olivine under hydrous conditions is constrained by our data with a Peierls stress of 4.2 ± 0.3 GPa. This value is much lower than those reported the Peierls stress for olivine under anhydrous conditions (~ 6 - 15 GPa, Evans and Goetze, 1979; Raterron et al., 2004; Mei at al., 2010), indicating a significant influence of water on the low-temperature plasticity of olivine. The low-temperature flow behavior of olivine under hydrous conditions quantified in this study provides a necessary constraint for modeling the dynamic activities occurring within lithospheric mantle especially for those regions with the presence of water such as beneath a mid-ocean ridge and along a subducting slab.

  7. 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.

  8. 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.

  9. New insights into the formation of fayalitic olivine from Allende dark inclusions

    NASA Astrophysics Data System (ADS)

    Varela, Maria E.; Zinner, Ernst; Kurat, Gero; Chu, Hao-Tsu; Hoppe, Peter

    2012-05-01

    Although considerable progress has been made in unraveling the origin(s) of fayalitic olivines in dark inclusions (DIs), many questions remain still unresolved and/or controversial. We combine a chemical and petrographic study of the Allende dark inclusion 4884-2B (AMNH, New York) and ATEM studies of a fragment of the dark inclusion Allende AF (NHM, Vienna) and discuss an alternative way in which fayalitic olivines could have formed. Allende dark inclusion 4884-2B contains a few aggregates with variable proportions of transparent and feathery olivine. Two such objects (aggregates A and B) are the focus of this study as they preserve glasses that can help in deciphering the nature of the processes involved during olivine growth and subsequent olivine transformation. The petrographic and chemical characteristics of aggregates A and B indicate that the forsteritic stack olivines may be pseudomorphs of clear olivine crystals. The ATEM studies in All-AF suggest that fayalitic olivines may be the result of secondary processes (e.g., metasomatic exchange reactions) operating in the solar nebula. Transformation may have occurred through the mediation of a dry gas phase involving nonvolatile major elements, such as Mg and Fe (e.g., Dohmen et al. 1998). This mechanism could reveal olivine growth patterns (e.g., stacked platelets due to a rapid growth regime) and may have contributed to the development of their fibrous aspect while preserving the shape (i.e., volume) of the crystals. This highly selective process did completely or partially transform ferromagnesian minerals, but affected the fine-grained mesostasis only slightly.

  10. 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

  11. Using Diffusion Modeling to Understand Ni Variability and Magmatic Histories of Hawaiian Olivines

    NASA Astrophysics Data System (ADS)

    Lynn, K. J.; Garcia, M. O.; Shea, T.

    2014-12-01

    The Ni content of olivine has been used extensively for inferring the source lithology, and depth and temperature of generation for basaltic magma in various tectonic settings. Conflicting interpretations have been derived using Ni because Hawaiian basalts show large variations in olivine Ni content (up to a factor of two) for a given forsterite (Fo). A detailed study of historical basalts at Kilauea volcano was undertaken using high-precision EPMA to better understand the cause of Ni variation in Hawaiian basalts. Experimental studies predict that Ni abundance in olivine should be positively correlated with Fo during growth. Element maps and core-rim transects of crystals strongly zoned in Fo show that many Kilauea olivines violate this relationship. They have decoupled profiles in which Fo decreases towards the rim by up to 5 mol% and Ni remains nearly constant. Here, we evaluate whether the Ni variability and Fo-Ni decoupling result from (1) diffusive re-equilibration and/or (2) sectioning effects rather than being primary growth features of those olivines. We used 1D diffusion modeling of Mg, Ni, and Ca from EPMA profiles to determine if decoupling is caused by diffusive re-equilibration. Calculated timescales (e.g. 2.2-3.1 yr) are in excellent agreement for all elements and transects within individual crystals, suggesting that the Fo-Ni decoupling is a primary growth feature of the olivine. Sectioning effects on Fo-Ni zoning were evaluated using 3D diffusion models of numerical olivines, which were constructed using realistic morphologies found in nature. Off-center and highly oblique sections have Fo and Ni extremums offset from the geometric center in 2D sections. Analyses of normally zoned olivine with decoupled Fo-Ni will yield similar Ni at variable Fo, introducing "Ni-enriched", low Fo data. These "Ni-enriched" olivine compositions may contribute to the range of interpretations derived from current datasets

  12. Olivine reactivity with CO 2 and H 2O on a microscale: Implications for carbon sequestration

    NASA Astrophysics Data System (ADS)

    Olsson, J.; Bovet, N.; Makovicky, E.; Bechgaard, K.; Balogh, Z.; Stipp, S. L. S.

    2012-01-01

    The silicate mineral olivine, (Mg,Fe)2SiO4, reacts exothermally with CO2 and forms secondary minerals, including carbonates. Therefore olivine reaction is a promising process for carbon sequestration, to convert carbon dioxide from the atmosphere to mineral form. The purpose of this study was (1) to explore the composition, structure and reactivity of olivine surfaces during exposure to air and to water at ambient conditions, (2) to investigate the effect of elevated CO2 pressure and temperature, and (3) to identify the secondary minerals. Olivine surfaces have been examined with atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), before and after reaction with CO2. Experiments were carried out in pure water equilibrated with CO2 at total pressures up to 80 bars, at temperatures 25 °C and 120 °C and both in the absence and presence of oxygen. New formation products appeared on the olivine surface as a homogeneous layer of bumps, less than 100 nm in diameter, within hours of exposure to air. Olivine crystals, exposed to water, dissolved and secondary minerals formed within days. Colonies of bacteria populated olivine surfaces on samples stored in water for more than 4 days at room temperature. Loosely attached material formed on olivine surfaces and could easily be scraped away with the AFM tip. A red precipitate formed when crystals where reacted at increased temperatures and CO2 partial pressures for less than 4 days. The new phases were identified as goethite, hematite, silica and carbonate minerals. Olivine surfaces oxidize and iron oxides form even when oxygen is absent, suggesting hydrolysis, where water is converted to hydrogen and oxygen.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. Oriented chromite-diopside symplectic inclusions in olivine from lunar regolith delivered by "Luna-24" mission

    NASA Astrophysics Data System (ADS)

    Khisina, N. R.; Wirth, R.; Abart, R.; Rhede, D.; Heinrich, W.

    2013-03-01

    Calcium-chromium rich lamellae in olivine grain No. 1611 from the Luna-24 regolith were studied with FEG-EMPA and TEM. The lamellae consist of a worm-like intergrowth of FeCr2O4 chromite (Chr) and CaMgSi2O6 diopside (Di), with a Chr:Di modal proportion of 1:3. The linear extension of the lamellae and crystallographic orientation relationships among the symplectite phases and the olivine suggest that the lamellae nucleated at deformation defects in the olivine host. Calcium depletion haloes surrounding the lamellae amount to about 75 μm and indicate that the chromite + diopside lamellae were formed by segregation of calcium and chromium from the host olivine into the lamellae without addition of calcium and/or chromium from outside the olivine. The segregation of calcium and chromium and, consequently, the growth of the symplectic lamellae were diffusion-controlled. The segregation of a calcium-chromium component from the host olivine was associated with oxidation of divalent to trivalent chromium. Oxidation was facilitated by dehydrogenation, which was driven by decompression and/or a change in redox potential. Hydrogen point defects in the original olivine with H+ substituting for divalent cations on the M-sites provided the necessary electron acceptors for the oxidation of chromium and after electron transfer left olivine as molecular H2. The internal microstructure of the lamellae suggests that exsolution of the calcium-chromium rich lamellae from the host olivine and formation of the chromite-diopside symplectic intergrowth occurred simultaneously. The time scale derived from diffusion modeling of the calcium depletion haloes around the lamellae indicates a thermal event on the order of several months to several hundred years at most. Symplectic inclusions found in olivine from lunar, martian and terrestrial rocks are similar with respect to their shape, crystallographic orientation relationships, and internal microstructure of the spinel

  19. Olivine CPO in non-deformed peridotite due to topotactic replacement of antigorite

    NASA Astrophysics Data System (ADS)

    Nagaya, Takayoshi; Wallis, Simon; Kobayashi, Hiroaki; Michibayashi, Katsuyoshi; Mizukami, Tomoyuki; Seto, Yusuke; Miyake, Akira; Matsumoto, Megumi

    2014-05-01

    Olivine crystallographic preferred orientation (CPO) is thought to be the main cause of seismic anisotropy in the mantle, and its formation is generally considered to be the result of plastic deformation of mantle by dislocation creep. Olivine CPO has been reproduced in laboratory deformation experiments and considerable success has been achieved in understanding the deformation conditions (e.g. stress, temperature and water content) under which different olivine CPO patterns develop. This opens the possibility of mapping conditions in the mantle using seismic anisotropy and has been the subject of considerable study. Here we report an alternative mechanism for olivine CPO without the need for deformation. This process may be important in understanding the seismic properties of mantle in convergent margins. Metamorphic studies show peridotite in the Happo area, central Japan, formed by the dehydration of antigorite-schist related to contact metamorphism around a granite intrusion. Both field and microstructural observations suggest the olivine has not undergone strong plastic deformation. This was confirmed by TEM work that shows the olivine has very low dislocation densities and lacks low angle tilt boundaries. Such tilt boundaries are general stable even after annealing. These features show that peridotite in the Happo area formed in the absence of solid-state deformation. The olivine of the Happo peridotite formed dominantly by the dehydration breakdown of antigorite schist. We propose that the olivine CPO formed as a result of topotactic replacement of antigorite by the newly formed olivine. EBSD measurements in samples where both antigorite and new olivine are present and in contact show a very close crystallographic relationship between the two minerals: the a-axes are parallel, and the b- and c-axes are perpendicular. We conclude the strong olivine CPO in the Happo area was inherited from the original CPO of the antigorite. Such a process is likely to also

  20. 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

  1. Water in Olivine and its High-Pressure Polymorphs

    NASA Astrophysics Data System (ADS)

    Thomas, S. M.; Jacobsen, S. D.; Bina, C. R.; Reichart, P.; Moser, M.; Dollinger, G.; Hauri, E. H.

    2014-12-01

    Theory and high-pressure experiments imply a significant water storage capacity of nominally anhydrous minerals (NAMs), such as olivine, wadsleyite and ringwoodite, composing the Earth's upper mantle and transition zone to a depth of 660 km. The presence of water, dissolved as OH into such nominally anhydrous high-pressure silicates, notably influences phase relations, melting behavior, conductivity, elasticity, viscosity and rheology. The first direct evidence for hydration of the transition zone has recently been reported by Pearson et al. (2014) and Schmandt et al. (2014). Knowledge of absolute water contents in NAMs is essential for modeling the Earth's interior water cycle. To take advantage of IR spectroscopy as highly sensitive water quantification tool, mineral-specific absorption coefficients are required. Such calibration constants can be derived from hydrogen concentrations determined by independent techniques, such as secondary ion mass spectrometry (SIMS), Raman spectroscopy or proton-proton(pp)-scattering. Broad beam pp-scattering has been performed on double-polished mm-sized mineral platelets (Thomas et al. 2008), but until recently analysis was not feasible for smaller samples synthetized in high-pressure apparati. Here we present first results from pp-scattering microscopy studies on μm-sized single crystals of hydrous olivine, wadsleyite and ringwoodite, which were synthesized at various pressure-temperature conditions in a multi-anvil press. The method allows us to quantify 3D distributions of atomic hydrogen in μm dimensions. These self-calibrating measurements were carried out at the nuclear microprobe SNAKE at the Munich tandem accelerator lab using a 25 MeV proton microbeam. We provide hydrogen depth-profiles, hydrogen maps and H2O concentrations. Pp-scattering data and results from independent Raman and SIMS analyses are in good agreement. Water contents for a set of high-pressure polymorphs with varying Fe-concentrations range from 0

  2. 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

  3. 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.

  4. 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

  5. Shallow crystallization of Kilauean olivines: Magma density and picritic eruptions

    SciTech Connect

    Anderson, A.T. Jr.; Brown, G.G. . Dept. of the Geophysical Sciences)

    1992-01-01

    Of 35 analyzed glass inclusions in olivine phenocrysts from the 1959 Kilauea Iki eruption, 23 formed at pressures less than 1 Kbar, 10 between 1 and 2 Kbar and 2 at pressures greater than 2 Kbar. The surprisingly topheavy distribution of formation pressures suggests that the 1959 magma rose rapidly to the upper parts of Kilauea's summit magma storage reservoir where cooling and crystallization dominantly occurred. The implication that the parental magma was buoyant relative to preexisting resident magma is consistent with an expected preeruptive bulk CO[sub 2] content of 0.3wt.% and petrographic evidence for turbulent mixing between parental and preexisting magma. That the 1959 magma was rich not only in crystals but also in gas, as evidenced by its high lava fountains, suggests that the storage time in the summit reservoir was too short for either crystals or gas to be lost. Therefore, the 1959 Kilauean magma probably is a near-parental magma that rose and formed a gas- and crystal-rich cap at the top of Kilauea's summit magma storage reservoir. Whether parental magma rises to the top or ponds at the base of the summit reservoir depends mainly on reservoir pressure and magma gas content. Consequently, it seems likely that the eruptive and degassing behavior of Kilauea is regulated in part by an interplay between the CO[sub 2] content of parental magma and the pressure at the base of the summit storage reservoir.

  6. 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.

  7. 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)

  8. Systematic Ion Irradiation Experiments to Olivine: Comparison with Space Weathered Rims of Itokawa Regolith Particles

    NASA Astrophysics Data System (ADS)

    Matsumoto, T.; Tsuchiyama, A.; Watanabe, N.; Yasuda, K.; Miyake, A.; Nakauchi, Y.; Okada, T.; Abe, M.; Yada, T.; Uesugi, M.; Karouji, Y.; Nakato, A.; Hashiguschi, M.; Kumagai, K.

    2015-11-01

    We performed H and He ion irradiation experiments using olivine fragments, in order to reveal formation time-scales of space weathered rims and formation processes of blisters by solar wind irradiation.

  9. Trace Element Distribution Between Olivine and Kirschsteinite in Angra Dos Reis

    NASA Technical Reports Server (NTRS)

    Fittipaldo, M. M.; Jones, R. H.; Shearer, C. K.

    2003-01-01

    The angrites are a small and enigmatic group of basaltic achondrites that possess unique mineralogical and chemical properties. The dominant mineralogy of the seven angrite members (Angra dos Reis, LEW 86010, LEW 87051, Asuka 881371, Sahara 99555, D Orbigny, and a new Moroccan member) is fassaite, olivine, and plagioclase. Angrites display a wide range of thermal histories, with Angra dos Reis (AdoR) exhibiting a cooling history different from that of the rapidly cooled members and from LEW86010, a more slowly cooled member. AdoR could represent either a cumulate or a porphyritic igneous rock that was later altered by metamorphism. We are re-examining the thermal history of AdoR in light of the more recently described angrite members. Our emphasis is a trace element study of low-Ca olivine, which we refer to as olivine, and high-Ca olivine, which we refer to as kirschsteinite, in AdoR.

  10. 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.

  11. Amoeboid Olivine Aggregates (AOAs) in the Efremovka (CVR) Chondrite: First SIMS Trace-Element Results

    NASA Astrophysics Data System (ADS)

    Ruzicka, A.; Floss, C.; Hutson, M.

    2008-03-01

    SIMS trace-element results for six inclusions in Efremovka imply that condensation was important in the formation of AOAs and that precursor compositions or mode of origin were different for olivine in AOAs and in chondrules.

  12. 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).

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. Olivine-rich rims surrounding chondrules in the Mokoia CV3 carbonaceous chondrite: Further evidence for parent-body processes

    NASA Astrophysics Data System (ADS)

    Tomeoka, Kazushige; Ohnishi, Ichiro

    2014-07-01

    Fine-grained rims surrounding chondrules and inclusions in the Mokoia CV3 carbonaceous chondrite can be divided into phyllosilicate-rich and olivine-rich types. We present a petrographic and electron microscopic study of the olivine-rich rims and their host objects (referred to as chondrules/olivine-rich rims). The olivine-rich rims consist mainly of Fe-rich olivine and very minor phyllosilicate (saponite). Their host chondrules contain minor saponite and phlogopite, which resulted from aqueous alteration of anhydrous silicates. Mineralogical and compositional characteristics of the chondrules/olivine-rich rims suggest that they experienced mild thermal metamorphic effects. The rims commonly contain veins of coarse-grained Fe-rich olivine, magnetite, and Fe-(Ni) sulfides. The chondrules show abundant evidence of alteration along their peripheries, and the alteration textures suggest a mechanism for rim formation by replacement of the chondrules. Initially, enstatite and opaque nodules preferentially reacted to form coarse, platy, Fe-rich olivine crystals, which were subsequently divided into finer grains. Forsterite was also replaced by Fe-rich olivine. As the alteration advanced, these Fe-rich olivines were disaggregated, mixed with simultaneously produced saponite, and formed rims. In contrast, the surrounding matrix shows no evidence of such alteration and metamorphism. These observations indicate that the chondrules/olivine-rich rims did not experience these secondary processes in their present setting. The results suggest that the chondrules/olivine-rich rims experienced extensive replacement reactions in an environment in which aqueous fluids existed but only in minor amounts. They have probably also undergone simultaneous and/or subsequent mild thermal metamorphism. We suggest that the chondrules/olivine-rich rims are actually clasts transported from a relatively dry region in the parent body that was different from the region where Mokoia was finally

  5. Modification of olivine surface morphology and reactivity by microbial activity during chemical weathering

    NASA Astrophysics Data System (ADS)

    Welch, Susan A.; Banfield, Jillian F.

    2002-01-01

    Prior transmission electron microscope studies showed that the surface geometry of olivine changes dramatically during natural chemical weathering. However, similar morphological evolution has not been reported in laboratory studies of olivine dissolution. In this study, we examined the development of fayalite (Fe 2SiO 4) surface morphology during both abiotic and biotic (using Acidithiobacillus ferrooxidans) laboratory dissolution experiments at an initial pH of 2.0. The fayalite came from Cheyenne Canyon, Colorado (Smithsonian # R 3516) and contains a few percent laihunite (olivine structure with ordered ferric iron and vacancies, ˜Fe 0.82+Fe 0.83+SiO 4). High-resolution field emission low voltage scanning electron microscope (SEM) characterization of all reacted samples showed etch patterns consistent with those reported from naturally reacted olivine. High-resolution transmission electron microscope (HRTEM) data demonstrated pervasive channeling on (001), with channel spacings that range down to < 10 nm. Formation of channels on (001) is probably initiated by preferential removal of cations from olivine M1 sites. Channeling confers at least an order of magnitude increase in surface area. Relict strips of olivine between channels contain laihunite layers that are oriented parallel to channel margins. X-ray diffraction analyses indicated that the relative abundance of laihunite is higher in reacted compared to unreacted samples. This result is consistent with prior studies of naturally weathered olivine that suggest that laihunite is far less readily dissolved than olivine. Samples reacted in the presence of A. ferrooxidans cells that enzymatically oxidized iron, or in solutions where ferric iron was added to simulate biological activity, dissolve at a much slower rate than samples reacted abiotically. We attribute suppression of the olivine dissolution rate to surface adsorption of Fe 3+. It is probable that ferric iron adsorption is controlled by M2 sites in

  6. 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.

  7. 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.

  8. The Effect of Titanium on Water Incorporation and Rheology of Olivine

    NASA Astrophysics Data System (ADS)

    Faul, U.; Farla, R. J.; Fitz Gerald, J. D.; Jackson, I.

    2011-12-01

    While there is general agreement that water significantly affects the physical properties of rocks, the water incorporation mechanism, particularly in olivine, is still under debate. Experiments with synthetic, polycrystalline olivine allow the controlled addition of trace elements as well as water. To this end we have conducted hotpressing and deformation experiments with solution-gelation derived Fo90 olivine doped with Ca and Ti. While the addition of Ca does not change the behavior relative to trace element-free solgel, trace amounts of titanium have a significant effect both on water incorporation and the rheology. Infrared spectroscopy suggests that from the presence of titanium water is retained in olivine during prolonged firing in a controlled atmosphere furnace at 1400C, while it is lost in Ti- free olivine. The experimental infrared spectra have the same two prominent absorption bands at 3572 and 3525 cm-1 as spectra of olivine from xenoliths. These bands indicate that water (hydrogen) is incorporated in a titanium-clinohumite type point defect. This defect is stable and significantly affects the physical properties of mantle rocks at low water contents. Diffusion creep rates are increased by about one order of magnitude in Ti-doped olivine, even if water contents are below detection levels. Experiments with different capsule materials also highlight their importance for water retention in the absence of buffers. The potential significance of the relationship between Ti abundance, water content and rheology for natural systems is shown for example by the correlation between Ti content and hydrogen in titanium clinohumite defects in cratonic xenoliths.

  9. 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.

  10. 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.

  11. The olivine-wadsleyite phase transformation in mantle peridotite

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Zhao, Y.; Wang, L.; Wang, Y.

    2009-12-01

    One of the most important goals in the study of the olivine (α) - wadsleyite (β) transformation is to understand the seismic discontinuity observed near the depth of 410 km in the Earth’s mantle. Although one school of thought attributes this discontinuity to radical chemical changes from lherzolite to picritic eclogite[1], the α-β transformation in an isochemical peridotitic mantle has widely been accepted as the underlying cause. If the latter interpretation is valid, the composition and temperature can be inferred by the depth and magnitude of the discontinuity, providing useful information for understanding the present state of the Earth’s transition zone. In spite of extensive experimental investigations of this transformation, most studies were conducted in the simple system Mg2SiO4-Fe2SiO4 and/or using the quenching technique[2]. No efforts have been directed to study the kinetic barrier of the α-β transformation under normal mantle conditions. In addition, recent studies have demonstrated increasing needs for the study of the α-β transformation in multi-component systems relevant to the Earth’s mantle[3,4]. We choose the KLB-1 spinel lherzolite, a xenolith from Kilborne Hole Crater in New Mexico USA, as starting material because it represents one of the most undepleted mantle compositions. The high P-T x-ray diffraction experiments were conducted using a two-stage multi-anvil press on beamline 13-BM-D of Advanced Photon source, Argonne National Laboratory. Phase identifications were made by observing the first appearance of a phase that was absent in the starting sample and by closely monitoring complete disappearance of a low-pressure phase from the assembly. In the presence of both α and β phases, transformation direction was identified by observing a significant change in the relative intensity between the two phases. Our results demonstrate the experimental feasibility of studying α-β transformation in complex systems and of resolving

  12. 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.

  13. 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

  14. Melt Connectivity and Its Effect on Grain Growth in Natural Olivine Aggregates: An Experimental Study

    NASA Astrophysics Data System (ADS)

    Hashim, L.; Sifre, D.; Précigout, J.; Gardés, E.; Le Trong, E.; Gaillard, F.

    2014-12-01

    To better constrain the rheology of the mantle, experimental studies on olivine grain growth have been conducted (Faul and Scott, 2006; Karato, 1989; Nichols and Mackwell, 1991) since the grain size is an important parameter under dynamic regimes (e.g. diffusion creep and grain boundary sliding). In order to better define the melt effect on the rheological response of a partially molten olivine aggregate, we have experimentally investigated the effect of melt on olivine grain growth and the connectivity of this melt phase. Experiments were performed in 3/4" piston cylinders at 500 MPa confining pressure, different temperatures (i.e. 1100°C, 1250°C and 1400°C) and four durations (1h, 12h, 72h and 15 days). Starting material was composed of natural San Carlos olivine (5 μmolivines were previously handpicked and annealed under controlled oxygen fugacity conditions close to the FMQ buffer. After the experiments, the melt connectivity was assessed through scanning electron microscope (SEM) images in backscattered electron mode. Electron backscatter diffraction (EBSD) maps of each sample were also collected in order to determine the olivine grain sizes as a function of time and melt content. References Faul, U. H., Scott, D., 2006. Grain growth in partially molten olivine aggregates. Contributions to Mineralogy and Petrology 151 (1), 101-111. Karato, S.-I., 1989. Grain growth kinetics in olivine aggregates. Tectonophysics 168 (4), 255-273. Nichols, S. J., Mackwell, S. J., 1991. Grain growth in porous olivine aggregates. Physics and Chemistry of Minerals 18 (4), 269-278. Sifré, D., Gardés, E., Massuyeau, M., Hashim, L., Hier-Majumder, S., Gaillard, F., 2014. Electrical conductivity during incipient melting in the oceanic low-velocity zone. Nature 509 (7498), 81-85.

  15. Impact of geoengineering with olivine dissolution on the carbon cycle and marine biology

    NASA Astrophysics Data System (ADS)

    Köhler, P.; Abrams, J.; Völker, C.; Wolf-Gladrow, D. A.; Hartmann, J.

    2012-04-01

    We investigate the potential of a specific geoengineering technique: the 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. If 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. These upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2 in examples for the rivers Amazon and Congo (Köhler et al., 2010). The secondary effects of the input of silicic acid connected with this approach leads in an ecosystem model (ReCOM2.0 in MITgcm) to species shifts aways from the calcifying species towards diatoms, thus altering the biological carbon pumps. Open ocean dissolution of olivine would sequestrate about 1 Pg CO2 per Pg olivine from which about 8% are caused by changes in the biological pumps (increase export of organic matter, decreased export of CaCO3). The chemical impact of open ocean dissolution of olivine (the increased alkalinity input) is therefore less efficient than dissolution on land, but leads due to different chemical impacts to a higher surface ocean pH enhancement to counteract ocean acidification. We finally investigate open ocean dissolution rates of up to 10 Pg olivine per year corresponding to geoengineering rates which might be of interest in the light of expected future emission (e.g. A2 scenario with emissions rising to 30 PgC/yr in 2100 AD). Those rates would still sequestrate only less than 20% of the emission until 2100, but would require that the nowadays available

  16. Interdiffusion of deuterium and hydrogen in olivine and enstatite: Initial results

    NASA Astrophysics Data System (ADS)

    Tyburczy, J. A.; Du Frane, W. L.; Sharp, T. G.

    2009-12-01

    Interdiffusion rates of hydrogen and deuterium in olivine and enstatite, the most abundant minerals in the upper mantle, will improve our understanding of point defects, and defect dominated processes such as electrical conductivity. Deuterium is interdiffused into San Carlos olivine and enstatite as a traceable species of hydrogen to simulate the process of hydrogen self diffusion. Experiments were performed on oriented single crystals of olivine, and unoriented grains of olivine and enstatite. The olivine samples underwent two annealing steps before the diffusion experiment. The first anneal was at 1-bar, 1300 °C at NNO oxygen fugacity for 16+ hrs to set the point defects. Olivine samples were then saturated with 75 +/- 15 ppm-wt H2O during a hydrothermal anneal in a H2O(100wt%) bath at temperatures ranging between 750-900 °C, 2 GPa, NNO, with the inclusion of enstatite to buffer silica. Enstatite grains did not undergo a dry 1-atm anneal and were saturated with 300 +/- 100 ppm-wt H2O. Finally, deuterium is interdiffused into the hydrated olivine and enstatite; samples were recovered and brought back to the same P-T conditions as saturation in a D2O(90wt%)/H2O(10wt%) bath. We used the Cameca 6f SIMS at ASU to measure hydrogen and deuterium across samples from each of these experiments, and fit interdiffusion coefficients to the resulting deuterium and hydrogen profiles. In olivine D[100] is 2.0e-12 m^2/s at 800 °C, 2GPa. Diffusion lengths in the [010] and [001] directions were only modestly larger than the spatial resolution of our technique. Using concentration boundary conditions from the better quality data in [100] diffusion profile, we estimate diffusion coefficients for the other orientations as ~3e-13 m^2/s [001] and ~5e-14 m^2/s [010]. These values are roughly 1 ½ -2 orders of magnitude lower than chemical diffusion in San Carlos olivine (Kohlstedt & Mackwell, 1998). Activation energies estimated over the temperature range 750 - 800 °C are

  17. Sulfide mineralization in magmas: Investigating the effect of re-equilibrating olivine xenocrysts

    NASA Astrophysics Data System (ADS)

    Currier, R. M.; Marsh, B. D.

    2011-12-01

    Large amounts of entrained olivine xenocrysts are common features of many mafic magmas. It is only natural that mantle derived melts mechanically destabilize and incorporate disaggregated wall rock material during ascension and transport. Bowen noticed this in 1928 and many subsequent studies at, for example, Kilauea have noted an abundance of these 'Tramp Crystals' in proportion to the eruptive flux. These olivines are distinguished by their high, nonequilibrium magnesium contents (Fo:88-92), and, due to the very fast interdiffusion rates of iron and magnesium in olivine (~10-7-10-9 mm2/s), these crystals are often rimmed in iron-rich olivine, or, if given enough time, become completely re-equilibrated with the surrounding melt. Because this exchange occurs in a finite volume of liquid, the composition of the liquid during xenocryst re-equilibration may be strongly affected and driven from its normal course of evolution. The magnitude of this change is clearly a function of the relative amount of xenocrysts and the compositional difference between liquid and crystals. Because mantle olivine is always more forsteritic than the equilibrium olivine composition of the liquid, re-equilibration of olivine increases the magnesium content and decreases the iron content of the liquid. A possible outcome is a decrease in the saturation point of sulfide. The saturation point of sulfide in magmas is sensitive to the concentration of iron. This is a fundamentally important consideration, given the fact that the PGE content of sulfides reflects the cumulative amount of magma the sulfide "sees," and higher temperature saturation greatly increases the odds of sulfide existence and longevity. Presented is a model predicting sulfide saturation with varying loads of xenocrystic olivine within a solidifying body. Even at high temperatures, reasonable fractions of xenocrysts can lower the sulfide saturation concentration over 200 ppm. The model is then compared to a world

  18. 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.

  19. 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.

  20. Measurement of activation volume for creep of anhydrous olivine at upper mantle pressures

    NASA Astrophysics Data System (ADS)

    Dixon, N. A.; Durham, W. B.; Kohlstedt, D. L.; Mei, S.; Xu, L.

    2012-12-01

    Olivine is the most abundant and likely the weakest phase in the upper mantle, and thus its rheological properties have a critical role in controlling convective flow in this region. A persistent obstacle to understanding the behavior of olivine in the mantle has been the difficulty of determining activation volume (V*), the influence of hydrostatic pressure on high-temperature creep. The bulk of previous studies examining V* were conducted at low pressure (<300 MPa) and over small pressure ranges in gas-medium deformation machines, limiting precision and raising questions about application to relevant geological conditions. For this study, we conducted numerous deformation experiments on dry polycrystalline olivine in the D-DIA apparatus to pressures 1.5 to 9 GPa at 1373 K. Stress and strain were measured in-situ with synchrotron x rays. Refinement of diffraction technique has allowed stress resolution of ±0.02 GPa. For the pressure range in this study, we have measured an average activation volume of about 11-17 cm3/mol for dry polycrystalline San Carlos olivine. This is a substantial pressure effect, representing a pressure-induced viscosity increase seven orders of magnitude from the base of the lithosphere to the bottom of the upper mantle. The diffraction technique used for stress measurement in these experiments also illuminates the relative strength of differently oriented grains in our polycrystalline sample, providing new experimental evidence for preferred dislocation slip systems in olivine at high pressure.

  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. 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.

  3. Modeling the creep properties of olivine by 2.5-dimensional dislocation dynamics simulations

    NASA Astrophysics Data System (ADS)

    Boioli, Francesca; Carrez, Philippe; Cordier, Patrick; Devincre, Benoit; Marquille, Matthieu

    2015-07-01

    In this work we performed 2.5-dimensional (2.5D) dislocation dynamics simulations coupling climb with the glide dislocation motion to model the creep behavior of olivine, one of the main component of the Earth's upper mantle. In particular, we present an application of this method to determine the creep strain rate in a material with high lattice resistance, such as olivine. We show that by including the climb mechanism we reach steady state creep conditions. Moreover, we find that a creep power law with a stress exponent close to 3 can be extracted from our simulations and we provide a model based on Orowan's law to predict the creep strain rates in the high temperature and low stress regime. The model presented is relevant to describe the plastic flow of olivine in the Earth's mantle deformation conditions and can be useful to derive the high temperature creep behavior of other materials.

  4. 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

  5. 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

  6. Unusual olivine and pyroxene composition in interplanetary dust and unequilibrated ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Klock, W.; Mckay, D. S.; Thomas, K. L.; Palme, H.

    1989-01-01

    The presence, in both a number of interplanetary dust particles (IDPs) and in meteorite matrices, of olivine and orthopyroxene grains, low in FeO but containing up to 5 wt pct MnO, is reported. The majority of olivines and pyroxenes in meteorites contain less than 0.5 wt pct MnO. The presence of these low-iron, manganese-enriched (LIME) olivines and pyroxenes in IDPs and meteorites may indicate a link between the origin and history of IDPs and the matrix material of primitive meteorites. The origin of the LIME silicates could be explained by condensation from a gas of solar composition. Forsterite is the first major silicate phase to condense from a solar nebula gas, and Mn, which is not stable as a metal under solar nebula conditions, would condense at about 1100 K as Mn2SiO4 in solid solution with forsterite.

  7. 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.

  8. 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

  9. Preferred Orientation Evolution of Olivine Grains as an Indicator of Change in the Deformation Mechanism

    NASA Astrophysics Data System (ADS)

    Lychagin, D. V.; Tishin, P. A.; Kulkov, A. S.; Chernyshov, A. I.; Alfyorova, E. A.

    2015-09-01

    The paper presents the results of investigations of deformed natural polycrystalline olivine. The relationship of the structure of polycrystalline olivine grains to three modal size distributions has been revealed. Grains of different size were observed to be strained at threshold temperatures of 950, 775, and 650°C. It has been demonstrated that the microstructure develops as the dislocation mechanism changes from diffusion creep to grain boundary sliding. The changes in deformation mechanisms promote the change in the preferred crystallographic orientations of olivine from type A to type D and then to type B. The relation of the transitions between different types of orientations to the conditions of deformation in the lower layers of the lithosphere at the plate boundaries is discussed.

  10. Unusual olivine and pyroxene composition in interplanetary dust and unequilibrated ordinary chondrites

    NASA Astrophysics Data System (ADS)

    Klock, W.; Thomas, K. L.; McKay, D. S.; Palme, H.

    1989-05-01

    The presence, in both a number of interplanetary dust particles (IDPs) and in meteorite matrices, of olivine and orthopyroxene grains, low in FeO but containing up to 5 wt pct MnO, is reported. The majority of olivines and pyroxenes in meteorites contain less than 0.5 wt pct MnO. The presence of these low-iron, manganese-enriched (LIME) olivines and pyroxenes in IDPs and meteorites may indicate a link between the origin and history of IDPs and the matrix material of primitive meteorites. The origin of the LIME silicates could be explained by condensation from a gas of solar composition. Forsterite is the first major silicate phase to condense from a solar nebula gas, and Mn, which is not stable as a metal under solar nebula conditions, would condense at about 1100 K as Mn2SiO4 in solid solution with forsterite.

  11. 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

  12. 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. PMID:26694202

  13. Natural type-C olivine fabrics in garnet peridotites in North Qaidam UHP collision belt, NW China

    NASA Astrophysics Data System (ADS)

    Jung, Haemyeong; Lee, Jaeseok; Ko, Byeongkwan; Jung, Sejin; Park, Munjae; Cao, Yi; Song, Shuguang

    2013-05-01

    Water is known to change the lattice-preferred orientation (LPO) of olivine, which significantly affects seismic anisotropy in the Earth's upper mantle. Research into the LPO of olivine in the deep interior of the Earth has been limited due to inadequate specimens. We report both the water-induced LPOs of olivine and the presence of large quantities of water inside olivine, enstatite, and garnet in garnet peridotites from the North Qaidam ultrahigh-pressure (UHP) collision belt in NW China. We show that the [001] axis of olivine is aligned subparallel to the lineation and that the [100] axis is strongly aligned subnormal to the foliation. This alignment is a known feature of type-C LPO of olivine formed experimentally under water-rich conditions (≥ 700 ppm H/Si) at high pressure and temperature. Enstatite possessed an LPO with the [001] axis aligned parallel to the lineation and the [100] axis aligned normal to the foliation. FTIR analysis of this specimen revealed that olivine contained concentrations of water up to 1130 ± 50 ppm H/Si in clean areas, whereas olivine, enstatite, and garnet contained considerably more water, i.e., 2600 ± 100 ppm H/Si, 5000 ± 100 ppm H/Si, and 21,000 ± 200 ppm H/Si, respectively, when exsolved inclusions were visible. Confocal micro-Raman spectroscopy of these exsolved inclusions revealed that they were composed of hornblende and amphiboles. Straight dislocations were also commonly observed in olivine and are characteristic of olivine that had been experimentally deformed under hydrous conditions. These observations suggest that the type-C LPO of olivine in the North Qaidam UHP belt formed under water-rich conditions.

  14. New Insights on the Rheology of Olivine Deformed under Lithospheric Temperature Conditions

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Rheology of mantle rocks at lithospheric temperatures remains poorly constrained, since most experimental studies on creep mechanisms of olivine single crystals ((MgFe)2SiO4, Pbnm) and polycrystalline olivine aggregates were performed at high-temperatures (T >> 1200oC). In this study, we report results from deformation experiments on oriented single crystals of San Carlos olivine and polycrystalline olivine aggregate at temperatures relevant of the uppermost mantle (ranging from 800o to 1090oC) in tri-axial compression. The experiments were carried out at a confining pressure of 300 MPa in a high-resolution gas-medium mechanical testing apparatus at various constant strain rates (from 7 x 10-6 s-1 to 1 x 10-4 s-1). Mechanical tests show that mantle lithosphere is actually weaker than previously inferred from the extrapolation of high-temperature experiments. In this study, we present characterization of dislocation microstructures based on transmission electron microscopy and electron tomography. It is shown that below 1000°C, dislocation activity is restricted to [001] glide with a strong predominance of {110} as glide planes. We observe recovery mechanisms which suggest that the mechanical properties observed in laboratory experiments represent an upper bound for the actual behavior of olivine under lithospheric mantle conditions. Moreover, the drastic reduction in slip system activity observed questions the ability of deforming olivine aggregates in the ductile regime at such temperatures. We show that ductility is preserved thanks to the activation of alternative deformation mechanisms in grain boundaries involving disclinations.

  15. Lithium partitioning between olivine and diopside at upper mantle conditions: An experimental study

    NASA Astrophysics Data System (ADS)

    Yakob, Jessica L.; Feineman, Maureen D.; Deane, James A.; Eggler, David H.; Penniston-Dorland, Sarah C.

    2012-05-01

    Experiments were conducted at 1.5 GPa and temperatures between 700 °C and 1100 °C in order to assess the equilibrium distribution of lithium between olivine and diopside in the upper mantle. Lithium in olivine and diopside from natural mantle xenoliths displays a broad array of apparent partition coefficients ranging from ~ 0.2 to 10. In addition, a strikingly large range of lithium isotope ratios is observed in olivine and diopside from mantle xenoliths, with ∆7Liol-di (= δ7Liol - δ7Lidi) ranging from nearly zero to greater than 20‰. Both of these observations might be explained if the distribution of Li between olivine and diopside is strongly temperature dependent at mantle conditions such that a change in temperature, i.e. cooling upon exhumation, initiates diffusive re-equilibration of Li between phases in the xenolith. Accompanying dynamic fractionation of 6Li from 7Li due to differing diffusion rates of the two isotopes could then be permanently recorded in the xenolith if its temperature drops below the closure temperature before a new equilibrium is reached. The results of this study indicate a partition coefficient for Li between olivine and diopside (DLiol/di) of 2.0 ± 0.2 that is independent of temperature (within the error of our analyses) over the range 700 °C to 1100 °C. This lack of temperature dependence holds true when data from previous experiments at temperatures as high as 1375 °C are considered. Thus it appears that closed-system diffusion of Li between olivine and diopside in response to changing temperature is not an appropriate explanation for the observed range of elemental and isotopic distributions in natural xenoliths. Other possible explanations include Li redistribution in response to changing oxygen fugacity in the system, or diffusive addition or subtraction of Li during open-system interaction with an infiltrating melt or fluid.

  16. 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.

  17. 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

  18. 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.

  19. 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

  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. PMID:19058996

  1. Development of olivine Crystal Preferred Orientation in Oshima peridotite body as a remnant of oceanic lithosphere

    NASA Astrophysics Data System (ADS)

    Tasaka, M.; Toriumi, M.; Wataru, N.

    2008-12-01

    To know the mantle flow kinematics, investigation of the seismic anisotropy is common method in upper mantle. Anisotropy is linked to crystal preferred orientations (CPOs) of olivine which is most abundant and weakest mineral in upper mantle. However the quantitative investigation analyses of natural CPO data have not succeeded yet. So, we must understand how olivine CPOs develops with strain in deformation settings. The Oshima peridotite body is the lower part of the Yakuno ophiolite in SW Japan (Ishiwatari, 1985a, b). This body consists dominantly of dunite and harzburgite deformed in upper mantle. This peridotites display various microstructures such as coarse grained granoblastic texture (0.7-1.0mm), elongated porphyroclastic texture (1.0mm-) and fine grained equigranular texture (0.1mm-). We analyzed CPOs of olivine using EBSD method. The results show that CPOs of olivine was formed by (0kl)[100] or (010)[100] slip system. In order to characterize the CPOs, we first determined the fabric strength and orientation distribution density of the principal crystallographic axes (J-index and M-index; Tommasi et al., 2000 and Skemer et al., 2005). According to those studies with increasing monotonously strain, the value of J- and M-index also increases. The Oshima peridotite body shows the various fabric strength from J=2.95 to 16.26 (M=0.040 to 0.384). On this presentation, we propose a new inversion method of mantle deformation by matching the model CPO patterns with natural CPOs in the Alpine type peridotites. Furthermore, we investigated two kind of angles of olivine together with CPOs at the same time to analyze CPOs development during mantle deformation. There are; (1) Angles between slip plane of each olivine grain and sample lineation. (2) Misorientation angles between adjacent olivine grains. The different angles between the slip plane of olivine grains and the rock lineation (1) are controlled by lattice rotation due to dislocation glide (Sevillano et al

  2. 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.

  3. 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.

  4. Deformation of olivine-orthopyroxene aggregates: Implications for the strength of the lithosphere

    NASA Astrophysics Data System (ADS)

    Farla, R.; Cai, Z.; Karato, S.

    2011-12-01

    In order for plate tectonics to occur on Earth, the base of the oceanic lithosphere must be relatively weak ("yield stress" less than ~200 MPa). Such a weak layer is not consistent with a model where homogeneous deformation of pure olivine by dislocation creep is assumed. Previous studies on orthopyroxene (opx) showed (i) opx (with certain orientations) has much lower strength than olivine at low temperature and (ii) recrystallized grain-size of opx is smaller than that of olivine. These observations suggest that opx might play an important role in reducing the strength of an olivine + opx mixture at lithospheric conditions. To explore this idea, we have started a series of experimental studies to investigate the rheological behavior of olivine + opx mixtures. The rheology of a synthetic coarse-grained aggregate (oli: 75%, opx: 25%), was explored at high confining pressure (1.5 GPa) in the Griggs-type apparatus to avoid opx transformation to proto-enstatite. The range of temperature was 900 - 1200C and deformation experiments were (nearly) constant strain-rate. In the first stage, relatively dry San Carlos olivine powders were encapsulated in nickel and hot-pressed in the Griggs apparatus at 1300C and 1.3 GPa for 7.5 hours to promote grain growth. A nearly homogeneous grain-size of 10 - 50 μm was obtained (to ensure dislocation creep during deformation). The hot-pressed pellet was subsequently cut into thin slices, 400 μm thick. Each slice was sandwiched between two grooved alumina pistons and again placed in a nickel capsule. The pressure medium used in these experiments was CsCl, which reduced friction considerably (in comparison to e.g. MgO) and provided a clear indication of the 'hit point' and improved stress estimation. At 1200C CsCl was mixed with MgO to minimize persuasive melting of the salt. Results have shown that the olivine - opx aggregate began to deform above 900C at high pressure. At 1000C deformation was accompanied by the onset of dynamic

  5. Water disequilibrium in olivines from Hawaiian peridotites: Recent metasomatism, H diffusion and magma ascent rates

    NASA Astrophysics Data System (ADS)

    Peslier, Anne H.; Bizimis, Michael; Matney, Mark

    2015-04-01

    Constraining the distribution and mobility of H in olivine, the main mineral of the upper mantle, is crucial to our understanding of Earth's geodynamics because this trace element influences melting, rheology, and electrical and thermal conductivities of peridotite. For this purpose, the olivines from fresh and well-characterized peridotite xenoliths from Salt Lake Crater and Pali (Oahu, Hawaii), representing samples of the oceanic mantle lithosphere, were analyzed by FTIR. Water concentrations decrease from core to edge and near fractures of olivine grains, and are best interpreted as H loss during xenolith ascent to the surface in its host magma. Diffusion modeling of these profiles allowed the calculation of diffusion times, which were in turn used to estimate the average ascent rates of the xenolith host nephelinite at 0.2-25.3 m s-1. These rates are similar to those of continental basaltic magmas. Diffusion modeling further shows that the water contents at the core of olivines are preserved mantle values and are heterogeneous within each xenolith. In addition, the discrepant behavior of the 3225 cm-1 OH band (due to H in a Mg vacancy) relative to the other OH bands (in particular the Ti-H defect) along profiles evidences that H is heterogeneously distributed amongst olivine defects. These defect profiles are modeled to calculate that the diffusion rate of the Mg-H defect is about 1.3-6.8 times faster than that of the Ti-H defect. The heterogeneous distribution of H in the mantle between olivine cores in single xenoliths and within olivine grains testifies of a state of disequilibrium for water in these samples. The Salt Lake Crater peridotite olivines record two processes; recent metasomatism by a melt bringing water followed by water loss during ascent in the host magma, neither having lasted long enough for water to reach equilibrium. The observed decoupling between the heterogeneous distribution of H and the homogeneous distribution of lithophile elements

  6. 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.

  7. 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

  8. Electrically driven green, olivine, and amber color nanopyramid light emitting diodes.

    PubMed

    Chang, Shih-Pang; Chang, Jet-Rung; Sou, Kuok-Pan; Liu, Mei-Chun; Cheng, Yuh-Jen; Kuo, Hao-Chung; Chang, Chun-Yen

    2013-10-01

    We report the fabrication and studies of electrically driven green, olivine, and amber color nanopyramid GaN light emitting diodes (LEDs). InGaN/GaN multiple quantum wells (MQWs) were grown on the nanopyramid semipolar facets. Compared with the commonly used (0001) c-plane MQWs, the semipolar facet has lower piezoelectric field, resulting in much faster radiative recombination efficiency. This is important for high In content MQWs. The measured internal quantum efficiencies for green, olivine, and amber color LED are 30%, 25%, and 21%, respectively. The radiative and non-radiative lifetime of the semipolar MQWs are also investigated. PMID:24104218

  9. Olivine-hosted melt inclusions as an archive of redox heterogeneity in magmatic systems

    NASA Astrophysics Data System (ADS)

    Hartley, M. E.; Shorttle, O.; Maclennan, J.; Moussallam, Y.; Edmonds, M.

    2014-12-01

    Crystal-hosted melt inclusions are able to preserve information about the geochemical diversity of melts present within magmatic systems, including information about both the oxygen fugacity (fO2) of their mantle source and the redox evolution of their carrier melt. However, the ferric iron proportions (Fe3+/ΣFe) measured in olivine-hosted melt inclusions are partially controlled by post-entrapment processes, such that inclusions may no longer preserve a record of the fO2 at which they were trapped. Post-entrapment crystallisation (PEC) of olivine onto the inclusion walls during cooling sequesters Fe2+ into olivine. Olivine-hosted melt inclusions may also maintain H2O and fO2equilibrium with their external environment via coupled proton and metal vacancy diffusion through the olivine crystal lattice. In this study we present a combination of XANES, major, trace and volatile element (C, H, S, F, Cl) analyses from a suite of 100 olivine-hosted melt inclusions from the AD 1783 Laki eruption, Iceland. The inclusions are hosted in Fo86-Fo68 olivines, and have experienced up to a maximum of 7% PEC. They preserve a diverse range of melt compositions similar to that seen in global mid-ocean ridge basalts. Composition-dependent CO2-H2O solubility models have been used to determine the pressures of inclusion trapping. Many of the melt inclusions have experienced diffusive H+ re-equilibration with their external environment: trace element depleted inclusions with low initial H2O concentrations have gained H+ via diffusive exchange with a more H2O-rich carrier melt, which is a consequence of concurrent mixing and crystallisation of diverse primary melt compositions in the Laki magmatic system. This sample set therefore presents a unique opportunity to deconvolve the post-entrapment crystallisation and diffusion processes that modify Fe3+/ΣFe in olivine-hosted melt inclusions, permitting the recovery of the true extent of magmatic redox variability present at the time of

  10. 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

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Moessbauer spectra of olivine-rich achondrites - Evidence for preterrestrial redox reactions

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Martinez, S. L.

    1991-01-01

    Moessbauer spectral measurements at 4.2 K were made on several ureilites and the two shergottites found in Antarctica, as well as two ureilite falls, three SNC meteorite falls, and two finds in order to distinguish products of preterrestrial redox reactions from phases formed during oxidative weathering on the earth. The spectra indicated that several ureilites contain major proportions of metallic iron, much of which resulted from preterrestrial carbon-induced reduction of ferrous iron in the outermost 10-100 microns of olivine grains in contact with carbonaceous material in the ureilites. The cryptocrystalline nature of these Fe inclusions in olivine renders the metal extremely vulnerable to aerial oxidation, even in ureilites collected as falls. It is inferred that the nanophase ferric oxides or oxyhydroxides identified in Brachina and Lafayette were produced by terrestrial weather of olivines before the meteorites were found. The absence of goethite in two olivine-bearing Antarctic shergottites suggests that the 2 percent ferric iron determined in their Moessbauer spectra also originated from oxidation on Mars.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. Measurement of activation volume for creep of dry olivine at upper mantle pressure

    NASA Astrophysics Data System (ADS)

    Dixon, N. A.; Durham, W. B.; Suzuki, A. M.; Mei, S.; Kohlstedt, D. L.; Hustoft, J. W.

    2011-12-01

    Olivine is the most abundant and weakest phase in the upper mantle, and thus its rheological properties have a critical role in controlling convective flow in this region. A resilient obstacle to understanding the behavior of olivine in the mantle has been the difficulty of determining activation volume (V*), the influence of hydrostatic pressure on flow strength. The bulk of previous studies examining V* were conducted at low pressure (<300 MPa) and small pressure ranges in gas-medium deformation apparatuses, limiting precision and raising questions about application to relevant geological conditions. For this study, we conducted deformation experiments on dry polycrystalline olivine in the D-DIA apparatus. The development of a new hybrid soft-fired pyrophyllite/mullite sample assembly allowed for a broadened pressure range (2-9 GPa), while stress and strain were measured in-situ with synchrotron x rays. Refinement in diffraction technique has allowed stress resolution of ±0.01 GPa. For the pressure range in this study, we have measured an average activation volume of about 17 cm^3/mol for dry polycrystalline San Carlos olivine. This is a substantial pressure effect, representing a pressure-induced viscosity increase of nearly 7 orders of magnitude from the base of the lithosphere to the bottom of the upper mantle.

  6. Crystal orientation results in different amorphization of olivine during solar wind implantation

    NASA Astrophysics Data System (ADS)

    Li, Yang; Li, Xiongyao; Wang, Shijie; Li, Shijie; Tang, Hong; Coulson, Ian M.

    2013-10-01

    Crystal orientation plays an important role in mineral amorphization during solar wind implantation. To discuss these effects, ion implantation experiments were carried out to irradiate natural olivine grains by 1 × 1017 cm-2 50 keV He+. Based on the olivine grains irradiated in our experiment, residual crystal planes have been identified by reference to the crystal plane's spacing shown in diffraction images. It is found that He+ ions injected along [010] damages the olivine structure more effectively than with other orientations and that this possibly relates to the higher atomic density and the vertical impact of the flux on MO6 (where M commonly represents Fe2+ and Mg2+) octahedra chains. Crystal planes perpendicular or approximately perpendicular to [010] may be destroyed easily during the early stages of irradiation, particularly for (040). However, crystal planes, such as (041), (021), (022), (120), and (140), parallel to [100] or [001] may survive until the final stages of olivine amorphization. These different characteristics affected by crystal orientation in ion implantation might help researchers to better understand the process of solar wind weathering and in dating the exposure time of lunar and asteroidal soil grains as well as interplanetary dust particles affected by the solar wind.

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. Spinels and oxygen fugacity in olivine-phyric and lherzolitic shergottites

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Herd, C. D. K.; Taylor, L. A.

    2003-12-01

    We examine the occurrences, textures, and compositional patterns of spinels in the olivine- phyric shergottites Sayh al Uhaymir (SaU) 005, lithology A of Elephant Moraine A79001 (EET-A), Dhofar 019, and Northwest Africa (NWA) 1110, as well as the lherzolitic shergottite Allan Hills (ALH) A77005, in order to identify spinel-olivine-pyroxene assemblages for the determination of oxygen fugacity (using the oxybarometer of Wood [1991]) at several stages of crystallization. In all of these basaltic martian rocks, chromite was the earliest phase and crystallized along a trend of strict Cr-Al variation. Spinel (chromite) crystallization was terminated by the appearance of pyroxene but resumed later with the appearance of ulvospinel. Ulvospinel formed overgrowths on early chromites (except those shielded as inclusions in olivine or pyroxene), retaining the evidence of the spinel stability gap in the form of a sharp core/rim boundary (except in ALH A77005, where subsolidus reequilibration diffused this boundary). Secondary effects seen in chromites include reaction with melt before ulvospinel overgrowth, reaction with melt inclusions, reaction with olivine hosts (in ALH A77005), and exsolution of ulvospinel or ilmenite. All chromites experienced subsolidus Fe/Mg reequilibration. Spinel-olivine-pyroxene assemblages representing the earliest stages of crystallization in each rock essentially consist of the highest-Cr#, lowest-fe# chromites not showing secondary effects plus the most magnesian olivine and equilibrium low-Ca pyroxene. Assemblages representing the onset of ulvospinel crystallization consist of the lowest-Ti ulvospinel, the most magnesian olivine in which ulvospinel occurs as inclusions, and equilibrium low-Ca pyroxene. The results show that, for early crystallization conditions, oxygen fugacity (fO2) increases from SaU 005 and Dhofar 019 (~QFM -3.8), to EET-A (QFM -2.8) and ALH A77005 (QFM -2.6), to NWA 1110 (QFM -1.7). Estimates for later conditions indicate

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. Partitioning of Ni between olivine and siliceous eclogite partial melt: experimental constraints on the mantle source of Hawaiian basalts

    NASA Astrophysics Data System (ADS)

    Wang, Zhengrong; Gaetani, Glenn A.

    2008-05-01

    Olivine is abundant in Earth’s upper mantle and ubiquitous in basaltic lavas, but rarely occurs in eclogite. Partial melts of eclogite are, therefore, not in equilibrium with olivine, and will react with peridotite as they migrate through the upper mantle. If such melts erupt at Earth’s surface, their compositions will be highly modified and they may be olivine-saturated. We investigated experimentally the reaction between olivine and siliceous eclogite partial melt, and determined element partitioning between olivine and the melt produced by this reaction. Our results demonstrate that mixing of reacted eclogite partial melt with primitive basalt is capable of producing the positive correlation between melt SiO2 content and olivine Ni content observed in some Hawaiian lavas. Experiments were carried out by equilibrating eclogite partial melt or basalt with San Carlos olivine at 1 bar and 1,201 1,350°C. Our results show that eclogite partial melts equilibrated with mantle olivine retain their high SiO2, low FeO and MgO characteristics. Further, olivine-melt partition coefficients for Ni measured in these experiments are significantly larger than for basalt. Mixing of these melts with primitive Hawaiian tholeiitic lavas results in crystallization of high-Ni olivines similar to those in Makapuu-stage Koolau lavas, even though the mixed magmas have only moderate Ni contents. This results from a hyperbolic increase of the Ni partition coefficient with increasing polymerization of the mixed melt. Note that while eclogite partial melt in contact with peridotite will equilibrate with pyroxene as well as olivine, this will have the effect of buffering the activity of SiO2 in the reacted melt at a higher level. Therefore, an eclogite partial melt equilibrated with harzburgite will have higher SiO2 than one equilibrated with dunite, enhancing the effects observed in our experiments. Our results demonstrate that an olivine-free “hybrid” pyroxenite source is not

  17. Crystallographic preferred orientations and melt-rock interactions : olivine-rich troctolites from IODP Hole U1309D

    NASA Astrophysics Data System (ADS)

    Drouin, M.; Ildefonse, B.; Hirth, G.; Waters, C. L.; Godard, M.

    2010-12-01

    IODP Expeditions 304-305 sampled the Atlantis Massif, an oceanic core complex located at 30°N in the inside corner of the intersection of the Mid-Atlantic Ridge with the Atlantis Fracture Zone. The most primitive end-members of the recovered gabbroic sequence, olivine-rich troctolites (ol > ~70%), have textures and geochemical compositions intermediate between those of mantle peridotites and primitive cumulates, indicative of melt impregnation processes (Drouin et al., 2009). Olivine-rich troctolites from Hole U1309D (about 5% of recovered rocks) display poikilitic textures, with olivine ranging from coarse-grained subhedral crystals, commonly containing well-developed subgrains, to medium-grained rounded crystals with fewer or no substructures. Olivine substructures reveal dislocation creep that is consistent with activation of the main high-temperature slip systems, dominantly (010)[100]. Olivine crystallographic preferred orientation is very weak, but generally shows a relatively stronger, uncommon [001] concentration (Drouin et al., 2010). These unusual olivine fabrics are interpreted as resulting from dunitisation and melt impregnation of a previously deformed olivine matrix; the solid olivine framework is eventually disrupted by olivine corrosion along grain and subgrain boundaries, and the high-temperature plastic fabric is modified in a liquid-dominated regime. Similar fabrics are described in impregnated peridotites from the mantle/crust transition zone in the Oman ophiolite. A reduction of fabric strength in the presence of melt is also documented in deformation experiments performed in a gas-medium high-pressure high-temperature vessel. Experiments were conducted with olivine + melt (10 to 30 wt%) isostatically hot-pressed initial material. The olivine crystallographic preferred orientation is weaker in deformed sampled than in the undeformed hot pressed material. We propose that very weak fabrics such as those measured in the Atlantis Massif olivine

  18. Petrogenesis of Apollo 12 mare basalts. Part 1: Multiple melts and fractional crystallization to explain olivine and ilmenite basalt compositions

    NASA Technical Reports Server (NTRS)

    Neal, Clive R.; Taylor, Lawrence A.

    1993-01-01

    Mare basalts returned by the Apollo 12 mission have been divided into 4 groups on the basis of mineralogy and whole-rock chemistry: olivine basalts; pigeonite basalts; ilmenite basalts; and feldspathic basalts. James and Wright and Rhodes et al. concluded that the olivine and pigeonite groups were co-magmatic and that the within group variations are due to fractional crystallization of olivine and minor Cr-spinel, with pigeonite replacing olivine in the pigeonite basalts. Rhodes et al. concluded that the parental compositions for these suites were probably represented by the vitrophyres, and the olivine basalts are comprised essentially of cumulates and the pigeonites of evolved end-members. However, Neal et al. have demonstrated, using trace-element considerations, that the Apollo 12 olivine and pigeonite suites are not related. The ilmenite basalts were studied extensively by Dungan and Brown who noted that both cumulates and evolved fractionates were present within this group. In their modeling, Dungan and Brown used the vitrophyre compositions as parents. Neal et al. demonstrated that the feldspathic suite was probably comprised of only one member - 12038. Herein, the ilmenite and olivine basalts are demonstrated to be the products of several non-modal partial melting events of a single source followed by closed-system fractional crystallization.

  19. Chemical zonation in olivine-hosted melt inclusions: A record of syn-eruptive cooling

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    During the last few minutes to ho