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Sample records for olivines limnpo4 lifepo4

  1. Distinct Configurations of Antisite Defects in Ordered Metal Phosphates: Comparison between LiMnPO4 and LiFePO4

    NASA Astrophysics Data System (ADS)

    Chung, Sung-Yoon; Choi, Si-Young; Lee, Seongsu; Ikuhara, Yuichi

    2012-05-01

    By using a combination of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, ab initio density-functional theory calculations, and neutron powder diffraction techniques, We have found completely different configurations of the antisite exchange defects in LiMnPO4 and LiFePO4, with a random distribution of the exchange pairs without aggregation in the former and with zigzag-type clustering behavior preferred in the latter. Recalling the compositional analogy and identical crystal structure of the two metal phosphates, such unexpectedly distinct arrangement of the same type of point defects is a notable structural aspect.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  3. Synthesis of Highly Crystalline Olivine-Type LiFePO4 Nanoparticles by Solution-Based Reactions

    NASA Astrophysics Data System (ADS)

    Kim, Donghan; Lim, Jinsub; Choi, Eunseok; Gim, Jihyeon; Mathew, Vinod; Paik, Younkee; Jung, Hongryun; Lee, Wanjin; Ahn, Docheon; Paek, Seungmin; Kim, Jaekook

    LiFePO4 nanocrystals were synthesized in various polyol media without any further post-heat treatment. The LiFePO4 samples synthesized using three different polyol media namely, diethylene glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol (TTEG), exhibited plate and rod-shaped structures with average sizes of 50-500 nm. The X-ray diffraction (XRD) patterns were indexed on the basis of an olivine structure (space group: Pnma). The samples prepared in DEG, TEG, and TTEG polyol media showed reversible capacities of 123, 155, and 166 mAh/g, respectively, at current density of 0.1 mA/cm2 with no capacity fading and exhibited excellent capacity retention up to the 50th cycle. In particular, the samples showed excellent performances at high rates of 30 and 60 C with high capacity retention. It is assumed that the nanometer size materials (~50 nm) possessing a highly crystalline nature may generate improved performance at high rate current densities.

  4. Rate-induced solubility and suppression of the first-order phase transition in olivine LiFePO4.

    PubMed

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

    2014-05-14

    The impact of ultrahigh (dis)charge rates on the phase transition mechanism in LiFePO4 Li-ion electrodes is revealed by in situ synchrotron diffraction. At high rates the solubility limits in both phases increase dramatically, causing a fraction of the electrode to bypass the first-order phase transition. The small transforming fraction demonstrates that nucleation rates are consequently not limiting the transformation rate. In combination with the small fraction of the electrode that transforms at high rates, this indicates that higher performances may be achieved by further optimizing the ionic/electronic transport in LiFePO4 electrodes. PMID:24707878

  5. Extended solid solutions and coherent transformations in nanoscale olivine cathodes.

    PubMed

    Ravnsbæk, D B; Xiang, K; Xing, W; Borkiewicz, O J; Wiaderek, K M; Gionet, P; Chapman, K W; Chupas, P J; Chiang, Y-M

    2014-03-12

    Nanoparticle LiFePO4, the basis for an entire class of high power Li-ion batteries, has recently been shown to exist in binary lithiated/delithiated states at intermediate states of charge. The Mn-bearing version, LiMn(y)Fe(1-y)PO4, exhibits even higher rate capability as a lithium battery cathode than LiFePO4 of comparable particle size. To gain insight into the cause(s) of this desirable performance, the electrochemically driven phase transformation during battery charge and discharge of nanoscale LiMn0.4Fe0.6PO4 of three different average particle sizes, 52, 106, and 152 nm, is investigated by operando synchrotron radiation powder X-ray diffraction. In stark contrast to the binary lithiation states of pure LiFePO4 revealed in recent investigations, the formations of metastable solid solutions covering a remarkable wide compositional range, including while in two-phase coexistence, are observed. Detailed analysis correlates this behavior with small elastic misfits between phases compared to either pure LiFePO4 or LiMnPO4. On the basis of time- and state-of-charge dependence of the olivine structure parameters, we propose a coherent transformation mechanism. These findings illustrate a second, completely different phase transformation mode for pure well-ordered nanoscale olivines compared to the well-studied case of LiFePO4. PMID:24548146

  6. 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

  7. Electrochemical Performance of Electrophoretically Deposited Nanostructured LiMnPO4-Sucrose Derived Carbon Composite Electrodes for Lithium Ion Batteries.

    PubMed

    Ravi, Soumya P; Praveen, P; Sreelakshmi, K V; Balakrishnan, A; Subramanian, K R V; Shantikumar, V; Lee, Y S; Sivakumar, N

    2015-01-01

    The present study reports an approach by which thin films of sucrose added olivine type LiMnPO4-Ccomposite and pristine LiMnPO4 is made by a technique of electrophoretic co-deposition in which pristine and composite samples were synthesized by a sol-gel route. These thin films with enhanced surface area is used to fabricate cathodes for rechargeable Li ion batteries. XRD confirms phase pure single crystalline orthorhombic structure. Transmission Electron Microscopy (TEM) images shows the carbon coating over LiMnPO4 and the particle size restricted in the nano regime. The presence of sp2 hybridized carbon on LiMnPO4 particles is confirmed by X-ray Photon spectroscopy (XPS). To explore the electrochemical behavior, cyclic voltammetry (CV) and cycling studies were performed. The specific capacity for LiMnPO4-C is found to be increased by 43% in comparison to the pristine LiMnPO4. It also exhibited 86% retention in capacity compared to the pristine LiMnPO4 (52%). The result indicates that a proper carbon coating can significantly improve the electronic conductivity and hence the specific capacity. PMID:26328437

  8. Enhanced Electrochemical Properties of LiMnPO4/C by Glucose-Assisted Polyol Synthesis.

    PubMed

    Song, Jinju; Gim, Jihyeon; Kim, Sungjin; Park, Wangeun; Jo, Jeonggeun; Kim, Jaekook

    2015-08-01

    Carbon-coated nano-sized LiMnPO4/C particles are synthesized by polyol method using low-cost glucose as the carbon source. The X-ray diffraction patterns of the synthesized samples are well indexed to the orthorhombic olivine-LiMnPO4 structure. The morphology studies using FE-SEM and HR-TEM images clearly illustrate thin layered carbon coatings on LiMnPO4 particles of sizes ranging between 50~100 nm. The LiMnPO4/C particles delivers an initial discharge capacity of 151 mA h g-1 at a current density of 1.6 mA g-1 in the voltage range of 2.5-4.3 V with impressive capacity retentions. PMID:26369197

  9. 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

  10. 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.

  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. Tunable morphology synthesis of LiFePO4 nanoparticles as cathode materials for lithium ion batteries.

    PubMed

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

    2014-06-25

    Olivine LiFePO4 with nanoplate, rectangular prism nanorod and hexagonal prism nanorod morphologies with a short b-axis were successfully synthesized by a solvothermal in glycerol and water system. The influences of solvent composition on the morphological transformation and electrochemical performances of olivine LiFePO4 are systematically investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and galvanostatic charge-discharge tests. It is found that with increasing water content in solvent, the LiFePO4 nanoplates gradually transform into hexagonal prism nanorods that are similar to the thermodynamic equilibrium shape of the LiFePO4 crystal. This indicates that water plays an important role in the morphology transformation of the olivine LiFePO4. The electrochemical performances vary significantly with the particle morphology. The LiFePO4 rectangular prism nanorods (formed in a glycerol-to-water ratio of 1:1) exhibit superior electrochemical properties compared with the other morphological particles because of their moderate size and shorter Li(+) ion diffusion length along the [010] direction. The initial discharge capacity of the LiFePO4@C with a rectangular prism nanorod morphology reaches to 163.8 mAh g(-1) at 0.2 C and over 75 mAh g(-1) at the high discharging rate of 20 C, maintaining good stability at each discharging rate. PMID:24892948

  13. 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

  14. Synthesis and characterization of LiFePO4 electrode materials coated by graphene

    NASA Astrophysics Data System (ADS)

    Tian, Zhe; Liu, Shanshan; Ye, Feng; Yao, Sijia; Zhou, Zhufa; Wang, Shumei

    2014-06-01

    Olivine-type LiFePO4/graphene composite materials were synthesized via a high temperature solid-state method. In this paper, the sintering process of LiFePO4 precursor was conducted simultaneously with the reduction of graphene oxide, and then LiFePO4 with a thin and homogeneous graphene-shell coating can be obtained. The effects of different graphene coating amount on the structure and electrochemical properties of LiFePO4 cathode were investigated. Test results indicated that LiFePO4 material modified with high electrical conductive graphene exhibited a morphology of uniform and fine spherical particles with high crystallinity. LiFePO4/graphene (92:8 wt.) cathode had the lowest charge transfer resistance among all tested samples. It delivered a capacity of 167 mAh g-1 at 0.1 C and could tolerate various discharge currents with a capacity decay rate of only 27.2% after cycled stepwise under 0.1 C, 2 C, 5 C for 15 times, respectively.

  15. Three-Dimensional LiMnPO4·Li3V2(PO4)3/C Nanocomposite as a Bicontinuous Cathode for High-Rate and Long-Life Lithium-Ion Batteries.

    PubMed

    Luo, Yanzhu; Xu, Xu; Zhang, Yuxiang; Pi, Yuqiang; Yan, Mengyu; Wei, Qiulong; Tian, Xiaocong; Mai, Liqiang

    2015-08-12

    Olivine-type LiMnPO4 has been extensively studied as a high-energy density cathode material for lithium-ion batteries. To improve both the ionic and electronic conductivities of LiMnPO4, a series of carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposites are synthesized by a facile sol-gel method combined with the conventional solid-state method. The optimized composite presents a three-dimensional hierarchical structure with active nanoparticles well-embedded in a conductive carbon matrix. The combination of the nanoscale carbon coating and the microscale carbon network could provide a more active site for electrochemical reaction, as well as a highly conductive network for both electron and lithium-ion transportation. When cycled at 20 C, an initial specific capacity of 103 mA h g(-1) can be obtained and the capacity retention reaches 68% after 3000 cycles, corresponding to a capacity fading of 0.013% per cycle. The stable capacity and excellent rate capability make this carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposite a promising cathode for lithium-ion batteries. PMID:26196544

  16. 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 agreement with experiments on large LiFePO4 single crystals. Third, we investigate why LiFePO4 can be charged and discharged rapidly despite having to undergo a first-order phase transition. Conventional wisdom dictates that a system with strong equilibrium Li segregation behavior requires both nucleation and growth in the charge and discharge process, which should impede the overall kinetics. Rather, through first-principles calculations, we determine the minimal energy required to access a non-equilibrium transformation path entirely through the solid solution. Not only does this transformation mechanism require little driving force, but it also rationalizes how a kinetically favorable but nonequilibrium path is responsible for the extremely high rate performance associated with this material. The consequences of a rapid non-equilibrium single-particle transformation mechanism on (dis)charging a multi-particle assembly, as is the case in porous electrodes, are discussed and compared to experimental observations. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu)

  17. 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

  18. 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.

  19. Self-assembled LiFePO4 nanowires with high rate capability for Li-ion batteries.

    PubMed

    Peng, Lele; Zhao, Yu; Ding, Yu; Yu, Guihua

    2014-08-28

    Controlling the dimensions in the nanometer scale of olivine-type LiFePO4 has been regarded as one of the most effective strategies to improve its electrochemical performance for Li-ion batteries. In this communication, we demonstrate a novel LiFePO4 nanoarchitecture, which is composed of self-assembled single-crystalline nanowires and exhibits good rate capability with a reversible capacity of ∼110 mA h g(-1) at a current rate of 30 C, and a stable capacity retention of ∼86% after 1000 cycles at a current rate of 10 C. PMID:25011485

  20. Synthesis of LiyMnSiOx and LiMnPO4 nanostructures

    NASA Astrophysics Data System (ADS)

    Milke, Bettina; Strauch, Peter; Antonietti, Markus; Giordano, Cristina

    2009-09-01

    Nanosized LiyMnSiOx and LiMnPO4 have been synthesized by a hydrothermal route. Simply by changing parameters such as metal precursors and/or template, high surface area LiyMnSiOx with different morphology and sizes were prepared, in particular hollow spheres and plate-like nanoparticles, however with poorly developed crystallinity. In the case of LiMnPO4, highly crystalline nanocrystals were prepared.Nanosized LiyMnSiOx and LiMnPO4 have been synthesized by a hydrothermal route. Simply by changing parameters such as metal precursors and/or template, high surface area LiyMnSiOx with different morphology and sizes were prepared, in particular hollow spheres and plate-like nanoparticles, however with poorly developed crystallinity. In the case of LiMnPO4, highly crystalline nanocrystals were prepared. Electronic supplementary information (ESI) available: FT-IR spectra of LiyMnSiOx prepared with different silica sources and different metal precursors; particles size distributions of LiyMnSiOx in the form of hollow spheres and plate-like nanoparticles; ICP technical details. See DOI: 10.1039/b9nr00149b

  1. First-principles studies of Mg-doped LiFePO4 for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Shi, Siqi; Zhang, Hua; Mei, Wai-Ning; Liu, Aifang; Lim, Khoon-Cheng

    2010-03-01

    We investigate the formation energy, crystal parameters and electronic properties of Mg-doped (Li site and Fe site) lithium iron orthophosphate (LiFePO4) by using the first-principles calculations. We noticed that the Mg ions are much more easier to be doped on Fe site than Li site. Comparing with the pure LiFePO4, we found the band gap of Mg-doped LiFePO4 is a little narrower than that of the pure one, indicating that the enhancement of the electronic conductivity upon doping is likely. Furthermore, we discovered that Mg doped on the Fe site causes the bond length to change, which is consistent with our experimental data. The reduction of the Mg-O bond length favors the formation of Li^+ diffusion channels, hence improves the ionic dynamic properties of the olivine LiFePO4. Mg-doped LiFePO4 has bigger electricity peak area that the pure one, which is an indication of improved ionic diffusion.

  2. 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

  3. 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.

  4. Characterization of the carbon coating onto LiFePO4 particles used in lithium batteries

    NASA Astrophysics Data System (ADS)

    Julien, C. M.; Zaghib, K.; Mauger, A.; Massot, M.; Ait-Salah, A.; Selmane, M.; Gendron, F.

    2006-09-01

    While nanosized ferromagnetic particles could poison the performance of the Li batteries containing phospho-olivine, the carbon-film coating the LiFePO4 particles has a beneficial effect on cycling life of the cells. In this paper, we present the properties of the carbon layer deposited at the surface of the LiFePO4 grains. Characteristics of the carbon layer are analyzed using scanning electron microscopy, high-resolution transmission scanning electron microscopy, Fourier transform infrared, and Raman scattering (RS) spectroscopy. The carbon deposit characterized by RS spectroscopy is hydrogenated with very small hydrogen/carbon ratio, so that it belongs to the family of the amorphous graphitic carbon. The carbon deposit is similar to that obtained by pyrolysis technique at high temperature. It is expected to have the same properties (small hardness, high electronic conductivity) that favor both the Li diffusion from the LiFePO4 bulk and the charge-discharge rate of the cell. A model for the Li-ion transport throughout the coating is given.

  5. Reaction mechanism and influence of the experimental variables for solvothermal synthesized LiMnPO4 nanoplates

    NASA Astrophysics Data System (ADS)

    Zhu, Kunlei; Zhang, Wenxuan; Du, Jiangyong; Liu, Xiaoyan; Tian, Jianhua; Ma, Huanmei; Liu, Shengzhong; Shan, Zhongqiang

    2015-12-01

    Plate-like LiMnPO4 nanomaterial for Li-ion batteries is synthesised successfully via a facile solvothermal process in mixed water-diethylene glycol (DEG) solvents at 190 °C for 3 h. Experimental variables, including reaction time, reaction temperature and reactant mole ratio, are discussed in detail. A tentative reaction mechanism is proposed on the basis of the time dependent trials. It is found that, with the increase of reaction temperature, the formation of LiMnPO4 phase is accelerated and the reaction for synthesizing LiMnPO4 can be finished in a shorter time. Studies on the effect of reactant mole ratio further support the proposed mechanism. The electrochemical properties of obtained LiMnPO4 are examined after a carbon coating process. Electrochemical tests show that the obtained LiMnPO4 at 190 °C for 3 h exhibits better electrochemical performances than the LiMnPO4 synthesized at 170 °C for 4.5 h or 150 °C for 6 h. It is clear that an improved electrochemical performance can be obtained with the increase of reaction temperature and the decrease of reaction time. This result provides us thoughts and guidance to optimize the reaction conditions by harmonizing the reaction temperature and reaction time, which is beneficial for the practical application.

  6. 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.

  7. 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

  8. 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 cathode exhibited outstanding electrochemical performances (92 mA h g-1 at 10 C) versus lithium. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00933b

  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. 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

  12. High-capacity cathodes for lithium-ion batteries from nanostructured LiFePO4 synthesized by highly-flexible and scalable flame spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Hamid, N. A.; Wennig, S.; Hardt, S.; Heinzel, A.; Schulz, C.; Wiggers, H.

    2012-10-01

    Olivine, LiFePO4 is a promising cathode material for lithium-ion batteries due to its low cost, environmental acceptability and high stability. Its low electric conductivity prevented it for a long time from being used in large-scale applications. Decreasing its particle size along with carbon coating significantly improves electronic conductivity and lithium diffusion. With respect to the controlled formation of very small particles with large specific surface, gas-phase synthesis opens an economic and flexible route towards high-quality battery materials. Amorphous FePO4 was synthesized as precursor material for LiFePO4 by flame spray pyrolysis of a solution of iron acetylacetonate and tributyl phosphate in toluene. The pristine FePO4 with a specific surface from 126-218 m2 g-1 was post-processed to LiFePO4/C composite material via a solid-state reaction using Li2CO3 and glucose. The final olivine LiFePO4/C particles still showed a large specific surface of 24 m2 g-1 and were characterized using X-ray diffraction (XRD), electron microscopy, X-ray photoelectron spectrocopy (XPS) and elemental analysis. Electrochemical investigations of the final LiFePO4/C composites show reversible capacities of more than 145 mAh g-1 (about 115 mAh g-1 with respect to the total coating mass). The material supports high drain rates at 16 C while delivering 40 mAh g-1 and causes excellent cycle stability.

  13. 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.

  14. Effects of Nb-doped on the structure and electrochemical performance of LiFePO4/C composites

    NASA Astrophysics Data System (ADS)

    Ma, Zhipeng; Shao, Guangjie; Wang, Guiling; Zhang, Ying; Du, Jianping

    2014-02-01

    The olivine-type niobium doping Li1-xNbxFePO4/C (x=0, 0.005, 0.010, 0.015, 0.025) cathode materials were synthesized via a two-step ball milling solid state reaction. The effects of Nb doping were charactered by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and galvanostatic charge-discharge. It is found that Nb doping enlarges the interplanar distance of crystal plane parallel to [0 1 0] direction in LiFePO4. In other words, it widens the one dimensional diffusion channels of Li+ along the [0 1 0] direction. Electrochemical test results indicate that the Li0.99Nb0.01FePO4/C composite exhibits the best electrochemical performance with initial special discharge capacity of 139.3 mA h g-1 at 1 C rate. The present synthesis route is promising in making the solid state reaction method more practical for preparation of the LiFePO4 material.

  15. The influence of improved carbon coating layer with nanometer-sized CeO2 interconnector on the enhanced electrochemical performance of LiMnPO4

    NASA Astrophysics Data System (ADS)

    Chen, Fang-Jie; Tao, Fen; Wang, Chun-Mei; Zhang, Wen-Long; Chen, Li

    2015-07-01

    The CeO2/C hybrid coated LiMnPO4 composites are prepared via a simple and effective wet chemical process followed by heat treatment at 550 °C. The nanometer-sized CeO2 acts as an interconnector in carbon network, and its influence on the electrochemical performance is investigated in detail. The 0.25 wt.% CeO2-modified LiMnPO4/C (sample-0.25) exhibits the highest discharge capacity and the best cycle life, which can deliver an initial capacity of 139.9 mAh g-1 at 0.1C and still retain a reversible capacity of 120.4 mAh g-1 after 50 cycles (capacity retention of 86.1%). While for pristine LiMnPO4/C (sample-0), only 94.4 mAh g-1 can be obtained at the 50th cycle, corresponding to 72.9% of its initial discharge capacity (129.5 mAh g-1). Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) results confirm that an integrated and hybrid CeO2/C coating layer is formed on LiMnPO4 surface and its existence has no influence on the structure of LiMnPO4. The reason for the improved electrochemical properties of the CeO2-modified LiMnPO4/C composites has also been studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements.

  16. 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.

  17. 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}.

  18. Lithium-Ion Insertion Kinetics of Na-Doped LiFePO4 as Cathode Materials for Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Yan-Rong; Zhang, Rui; Deng, Li; Yi, Ting-Feng; Ye, Ming-Fu; Yao, Jin-Han; Dai, Chang-Song

    2015-03-01

    Na-doped Li1- x Na x FePO4 ( x = 0, 0.05, 0.1, and 0.2) materials were synthesized by a simple high-temperature solid-state method. The structure, morphology, and kinetic performances of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). XRD indicates that all samples are in accordance with the standard LiFePO4 with olivine structure. SEM reveals that the particle size of all samples is about 1 to 2 µm. CV exhibits that Na doping obviously improves the reversibility and dynamic behaviors of lithium intercalation and deintercalation. EIS shows that Na doping decreases the charge transfer resistance of LiFePO4 and improves the lithium diffusion coefficients. It can be concluded that Na doping results in lower electrode polarization and higher lithium-ion diffusion coefficient, which can effectively improve the kinetic performance of LiFePO4.

  19. 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-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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr04611g

  20. 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

  1. 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.

  2. [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

  3. 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.

  4. 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

  5. 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.

  6. 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

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

    PubMed Central

    2016-01-01

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

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

    PubMed

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

    2016-02-17

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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

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

    PubMed

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

    2013-05-01

    Porous LiFePO4/C microspheres were synthesized by a novel hydrothermal reaction combined with high-temperature calcinations. The morphology of the prepared material was investigated by field-emission scanning electron microscopy. Porous microspheres with diameters around 1-3 microm were obtained, which consisting of primary LiFePO4 nanoparticles. The electrochemical performances of the as-prepared LiFePO4 microspheres were evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge cycling. The carbon coated LiFePO4 microspheres showed lower polarization, higher rate capability, and better cycling stability than that of pristine LiFePO4 microspheres, indicating the potential application as the cathode material for high-power lithium ion batteries. PMID:23858922

  16. 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.

  17. Chemically grafted carbon-coated LiFePO4 using diazonium chemistry

    NASA Astrophysics Data System (ADS)

    Delaporte, Nicolas; Perea, Alexis; Amin, Ruhul; Zaghib, Karim; Bélanger, Daniel

    2015-04-01

    The effect of surface functionalization of aminophenyl and bromophenyl groups on carbon-coated LiFePO4 and the electrochemical properties of composite electrode containing these materials are reported. The functionalization was performed by spontaneous reduction of the corresponding in situ generated diazonium ions. The resulting chemically grafted LiFePO4/C materials were characterized by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. XRD analyses indicated the cathode material was partially oxidized. Thermogravimetric and elemental analyses revealed the loading of grafted molecules was between 0.2 and 1.1 wt.% depending on the reaction conditions. Interestingly, the electrochemical performances of the modified LiFePO4/C are not adversely affected by the presence of either aminophenyl and bromophenyl groups at the carbon surface, and in fact the grafted LiFePO4/C displayed slightly superior discharge capacity at the highest C rate investigated for a low loading of organic molecules.

  18. 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.

  19. 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.

  20. 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.

  1. Investigation of charge transfer kinetics of Li-Intercalation in LiFePO4

    NASA Astrophysics Data System (ADS)

    Heubner, C.; Schneider, M.; Michaelis, A.

    2015-08-01

    Recent studies point out contradictions between classical Butler-Volmer kinetics and the charge transfer kinetics of lithium intercalation in host materials. In this work the charge transfer kinetics of lithium intercalation in LiFePO4 are investigated using current controlled electrochemical impedance spectroscopy with varying amplitudes. The results point out a significant impact of ohmic and diffusion contributions to the total overpotential which is normally extracted from constant current charging - discharging experiments to determine Tafel-plots, exchange currents and charge transfer coefficients. By the accurate separation of the activation overpotential from the total overpotential the authors are able to show that the charge transfer kinetics of lithium intercalation in LiFePO4 perfectly obey the Butler-Volmer equation.

  2. 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.

  3. Monodisperse porous LiFePO4 microspheres for a high power Li-ion battery cathode.

    PubMed

    Sun, Chunwen; Rajasekhara, Shreyas; Goodenough, John B; Zhou, Feng

    2011-02-23

    A novel solvothermal approach combined with high-temperature calcinations was developed to synthesize on a large scale LiFePO(4) microspheres consisting of nanoplates or nanoparticles with an open three-dimensional (3D) porous microstructure. These micro/nanostructured LiFePO(4) microspheres have a high tap density and, as electrodes, show excellent rate capability and cycle stability. PMID:21268579

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  5. 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.

  6. 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.

  7. 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

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

    PubMed

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

    2016-04-13

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

  9. 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.

  10. LiFePO 4 safe Li-ion polymer batteries for clean environment

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Charest, P.; Guerfi, A.; Shim, J.; Perrier, M.; Striebel, K.

    The performance of natural graphite-fibers/PEO-based gel electrolyte/LiFePO 4 cells (7 mAh, 4 cm 2) is reported. The gel polymer electrolytes were produced by electron-beam irradiation and then soaked in a liquid electrolyte. The natural graphite-fiber composite anode in gel electrolyte containing 1.5 M LiFSI-EC/GBL (1:3) exhibited high reversible capacity (361 mAh g -1) and high Coulombic efficiency (92%). The LiFePO 4 cathode in the same gel polymer exhibited a reversible capacity of 161 mAh g -1 and 93% Coulombic efficiency. A 1.5 M solution of LiFSI in ethylene carbonate (EC)/γ-butyrolactone (GBL) (1:3, v/v) mixed solvent is advantageous for use as the electrolyte in the laminated film bag because of its high flame point (135 °C), high boiling point (219 °C), low vapor pressure and high conductivity (10.2 mS cm -1 at 20 °C). The Li-ion gel polymer battery shows a very low capacity fade of 5% after 500 cycles and also has high-rate capability. The Li-ion gel polymer cell using LiFePO 4 cathodes is suitable for HEV applications.

  11. 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.

  12. 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.

  13. Synthesis and Characterization of LiFePO4 Cathode with Fe:P Deficiency for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Fang, Hui; Neeley, Travis; Hill, Jacob; Liang, Gan

    2009-10-01

    LiFePO4 with Fe:P deficiency has been demonstrated a promising cathode material of lithium ion battery for fast rate, high capacity applications. In this study, LiFePO4 with various amount of Fe:P deficiency are synthesized using high energy ball milling and temperature controlled sintering under reduced gas. X-ray diffraction, X-ray absorption, cyclic voltammetry and constant current charge/discharge measurements are employed to characterize the structural and electrochemical properties of the samples. The effects brought by Fe:P deficiency on charger/discharge rate and capacity will be discussed and presented.

  14. 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

  15. 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.

  16. 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

  17. Effect of carbon source on the morphology and electrochemical performances of LiFePO4/C nanocomposites.

    PubMed

    Liu, Shuxin; Wang, Haibin; Yin, Hengbo; Wang, Hong; He, Jichuan

    2014-03-01

    The carbon coated LiFePO4 (LiFePO4/C) nanocomposites materials were successfully synthesized by sol-gel method. The microstructure and morphology of LiFePO4/C nanocomposites were characterized by X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The results showed that the carbon layers decomposed by different dispersant and carbon source had different graphitization degree, and the sugar could decompose to form more graphite-like structure carbon. The carbon source and heat-treatment temperature had some effect on the particle size and morphology, the sample LFP-S700 synthesized by adding sugar as carbon source at 700 degrees C had smaller particle size, uniform size distribution and spherical shape. The electrochemical behavior of LiFePO4/C nanocomposites was analyzed using galvanostatic measurements and cyclic voltammetry (CV). The results showed that the sample LFP-S700 had higher discharge specific capacities, higher apparent lithium ion diffusion coefficient and lower charge transfer resistance. The excellent electrochemical performance of sample LFP-S700 could be attributed to its high graphitization degree of carbon, smaller particle size and uniform size distribution. PMID:24745239

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  20. 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.

  1. 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.

  2. 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.

  3. Li-ion Batteries: Ultralong Lifespan and Ultrafast Li Storage: Single-Crystal LiFePO4 Nanomeshes (Small 4/2016).

    PubMed

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

    2016-01-01

    A low crystal mismatch strategy to fabricate novel LiFePO4 nanomeshes is presented by Y. Wang and co-workers on page 516. The LiFePO4 nanomesh is characterized by numerous advantages, such as mesoporous structure, enhanced structural integrity, and a shortened Li ion diffusion pathway along the [010] direction. Furthermore, the obtained LiFePO4 nanomesh can be applied in lithium ion batteries as an excellent cathode for fast extraction-insertion of lithium ions and exhibits outstanding electrochemical performance. PMID:26797531

  4. 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.

  5. 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.

  6. 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.

  7. Optimization of reaction condition for solid-state synthesis of LiFePO 4-C composite cathodes

    NASA Astrophysics Data System (ADS)

    Zhang, S. S.; Allen, J. L.; Xu, K.; Jow, T. R.

    We optimized synthesis condition of LiFePO 4-C composites by solid-state reaction of LiH 2PO 4 and FeC 2O 4·2H 2O in the presence of carbon powder. The preparation was conducted under a N 2 flow through two heating steps. First, the starting materials were thoroughly mixed in a stoichiometric ratio and decomposed at 350-380 °C to form the precursor. Second, the resulting precursor was heated at a high temperature to form the crystalline phase LiFePO 4. For formation of the precursor, the optimized temperature was 350 °C for LiFePO 4 and 380 °C for LiFePO 4-C composites, respectively. For formation of crystalline phase composites, the optimized condition was to heat the precursor in a pelletized form at 800 °C for 5 h, and the optimized content of carbon was 3-10 wt.%. In composites, the carbon not only increases the rate capability, but also enhances capacity stability. We found that capacity of the composites increases with specific surface area of carbon. The best result was observed from a composite made of 8.7 wt.% of black pearls BP 2000 having a specific surface area of 1500 m 2 g -1. At room temperature and low current rate (0.02 C), such a composite shows a specific capacity of 159 mAh g -1. Electrochemical properties and cycling performance of the optimized composite also were evaluated.

  8. 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

  9. 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

  10. 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.

  11. A synthesis of LiFePO4 starting from FePO4 under reducing atmosphere

    NASA Astrophysics Data System (ADS)

    Prosini, Pier Paolo; Cento, Cinzia; Masci, Amedeo; Carewska, Maria; Gislon, Paola

    2014-06-01

    A fast and easy way to produce LiFePO4 starting from FePO4, used as iron and phosphorus source, is proposed. 5% hydrogen is employed as a reducing agent and various compounds containing lithium as lithiation agents. The selected lithiation agents included: LiCl, CH3COOLi, LiOH, Li2S, LiH, and Li2CO3. Solid state synthesis is used for the LiFePO4 preparation and the so obtained materials are structurally characterized by XRD. The materials are used to fabricate composite electrode and their specific capacity is evaluated by low rate galvanostatic charge/discharge cycles (C/10 rate). Among the various lithium salts, the acetate give rise to the LiFePO4 with the best electrochemical performance. The morphology of this material is further investigated by SEM microscopy and the specific capacity is evaluated as a function of the discharge rate and the cycle number.

  12. X-ray Diffraction and Polarized X-ray Absorption Study of Single Crystal LiFePO4

    NASA Astrophysics Data System (ADS)

    Liang, Gan; Benson, Ron; Li, Jiying; Vaknin, David; Croft, Mark

    2006-10-01

    Large size LiFePO4 single crystals have been grown by standard flux growth technique with the LiCl as the flux. Single crystal x-ray diffraction (XRD) and synchrotron polarized x-ray absorption spectroscopy (XAS) measurements have been performed on the crystals. The XRD measurements were performed at T = 293 K using Mo K? radiation (? = 0.7107) to a resolution corresponding to sin?/? = 0.6486 -1, with 2?max = 54.9 . A total number of 1330 reflections were processed with 350 unique data. The obtained crystal structure data were the following: lithium iron (II) phosphate, LiFePO4, orthorhombic, space group Pnma, lattice constants: a = 10.3172 (11) , b = 6.0096(8) , c = 4.6775 (4) , Z = 4, formula weight: 157.76, density: 3.613, ? = 55.562 cm-1. The bond lengths between Fe and O and between P and O were obtained. The polarized XAS was performed at the Fe K-edge with the x-ray E-vector along the a-, b-, and c-axis. The XAS results show that the Fe ions in the LiFePO4 single crystals are divalent. We also observed a big shift in both the energies of the pre-edge 1s -> 3d transition feature and the main edge when the polarization direction of the E-vector changes from along a-axis to along c-axis.

  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 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.

  15. 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

  16. A molecular dynamics simulation study of LiFePO4/electrolyte interfaces: structure and Li+ transport in carbonate and ionic liquid electrolytes.

    PubMed

    Smith, Grant D; Borodin, Oleg; Russo, Salvy P; Rees, Robert J; Hollenkamp, Anthony F

    2009-11-14

    We have performed atomistic molecular dynamics (MD) simulations of the (010) surface of LiFePO(4) in contact with an organic liquid electrolyte (OLE), ethylene carbonate : dimethyl carbonate (3 : 7) with approximately 1 mol kg(-1) LiPF(6), and an ionic liquid-based electrolyte (ILE), 1-ethyl 3-methyl-imidazolium: bis(fluorosulfonyl)imide (EMIM(+) : FSI(-)) with approximately 1 mol kg(-1) LiFSI. Surface-induced structure that extends about 1 nm from the LiFePO(4) surface was observed in both electrolytes. The electrostatic potential at the LiFePO(4) surface was found to be negative relative to the bulk electrolyte reflecting an excess of negative charge from the electrolyte coordinating surface Li(+). In the ILE system negative surface charge is partially offset by a high density of EMIM(+) cations coordinating surface oxygen. The electrostatic potential exhibits a (positive) maximum about 3 A from the LiFePO(4) surface which, when combined with the reduced ability of the highly structured electrolytes to solvate Li(+) cations, results in a free energy barrier of almost 4 kcal mol(-1) for penetration of the interfacial electrolyte layer by Li(+). The resistance for bringing Li(+) from the bulk electrolyte to the LiFePO(4) surface through this interfacial barrier was found to be small for both the OLE and ILE. However, we find that the ability of EMIM(+) cations to donate positive charge to LiFePO(4)/electrolyte interface may result in a significant decrease in the concentration of Li(+) at the surface and a corresponding increase in impedance to Li(+) intercalation into LiFePO(4), particularly at lower temperatures. PMID:19851568

  17. 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.

  18. 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

  19. 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

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

    PubMed

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

    2014-09-10

    Much attention has been paid to metastable materials in the lithium battery field, especially to nanocrystalline and amorphous materials. Nonetheless, fundamental issues such as lithium potential variations have not been pertinently addressed. Using LiFePO4 as a model system, we inspect such lithium potential variations for various lithium storage modes and evaluate them thermodynamically. The conclusions of this work are essential for an adequate understanding of the behavior of electrode materials and even helpful in the search for new energy materials. PMID:25133677

  1. Comparison between different LiFePO 4 synthesis routes and their influence on its physico-chemical properties

    NASA Astrophysics Data System (ADS)

    Franger, Sylvain; Le Cras, Frédéric; Bourbon, Carole; Rouault, Hélène

    LiFePO 4 powders were synthesized under several different conditions (solid state reactions at high temperatures, co-precipitation in aqueous medium, hydrothermal synthesis or mechanochemical activation). The samples were characterized by X-ray diffraction (XRD), chemical titration and their electrochemical performance were investigated in terms of cycling behavior. We also report, in this work, the benefit of introducing an electronic conductor precursor (typically a sucrose) during or after the synthesis in order to overcome the poor charge transfer associated with the lithium iron phosphate.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  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. 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.

  5. Optimization of multicomponent aqueous suspensions of lithium iron phosphate (LiFePO4) nanoparticles and carbon black for lithium-ion battery cathodes.

    PubMed

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

    2013-09-01

    Addition of polyethyleneimine (PEI) to aqueous LiFePO4 nanoparticle suspensions improves stability and reduces agglomerate size, which is beneficial to lithium-ion battery cathode manufacturing. This research examines the effect of both PEI concentration and molecular weight (MW) on dispersing LiFePO4 and Super P C45 in multicomponent aqueous suspensions. It is demonstrated that the optimal conditions for obtaining stable suspensions with minimal agglomerate size are 1.5 wt% PEI with MW=2000 g mol(-1) and 5.0 wt% PEI with MW=10,000 g mol(-1) for LiFePO4 and Super P C45, respectively. The mixing sequence also affects rheological properties of these suspensions. It is found that dispersing the LiFePO4 and Super P C45 separately yielded suspensions with superior properties (Newtonian rheological behavior, smaller agglomerate size, improved settling, etc.). In particular, dispersing the LiFePO4 prior to the Super P C45 when making the final multicomponent suspension is found to be beneficial, which was evidenced by higher half-cell discharge capacity. PMID:23764234

  6. 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

  7. 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.

  8. Optical and surface properties of LiFePO4 thin films prepared by RF magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Volkan, Şenay; Özen, Soner; Pat, Suat; Korkmaz, Şadan

    2015-03-01

    LiFePO4 thin films with thickness values of 65 nm and 70 nm were deposited onto glass substrates by RF magnetron sputtering, using a LiFePO4 target in the argon atmosphere. A comprehensive study of the optical properties was performed and the dispersions of the constants were determined. The transmittance and absorbance spectra were measured in the wavelength range of 400-1000 nm. The films showed optical transmittance over 90% in the visible range. The optical band gap value of the films was evaluated as 3 eV. The refractive index value of the films is 1.63 at λ = 550 nm. AFM micrographs indicate smooth surface with low values ofroot mean square roughness. Contact angle measurements of several testing liquids were used to characterize each sample in terms of wettability. The films are hydrophilic as observed from contact angle measurements. The surface free energy of the film surfaces and their components (dispersive and polar) were calculated from the contact angle data using the different theories available in the literature.

  9. 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.

  10. 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.

  11. 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.

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

    SciTech Connect

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

    2007-09-19

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

  13. Enhanced low temperature electrochemical performances of LiFePO4/C by surface modification with Ti3SiC2

    NASA Astrophysics Data System (ADS)

    Cai, Guanglan; Guo, Ruisong; Liu, Li; Yang, Yuexia; Zhang, Chao; Wu, Chen; Guo, Weina; Jiang, Hong

    2015-08-01

    Ti3SiC2-modified LiFePO4/C cathode materials are prepared via a suspension mixing method followed by heat-treatment at 400 °C. The galvanostatic electrochemical measurements indicate that 4 wt% Ti3SiC2-modified LiFePO4/C exhibits the best electrochemical performances in the voltage range of 2.0-4.2 V. The sample shows the highest initial discharge capacity of 116.0 mAh g-1 at the rate of 0.1 C at -20 °C. And it keeps a capacity retention of 97.0% at 1 C at -10 °C after 100 cycles, higher than 81.2% for LiFePO4/C at the same conditions. Furthermore, Ti3SiC2-modified LiFePO4/C samples deliver lower charge-transfer resistance and higher diffusion coefficient of Li+ compared with the pristine LiFePO4/C, especially the 4 wt% Ti3SiC2-modified LiFePO4/C sample exhibits the lowest charge-transfer resistance and highest diffusion coefficient of Li+ among all the four samples. The improved electrochemical performances can be attributed to the lower charge transfer resistance and higher diffusion coefficient of lithium ions resulted from the modification of appropriate amount of Ti3SiC2. Besides, a series of electrochemical results show that the performances of the electrodes with 10 wt% super-P are superior to those of the electrodes with 5 wt% super-P.

  14. 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

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

    PubMed

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

    2014-07-21

    The present review reports the characterization and control of interfacial processes occurring on olivine LiFePO(4) and layered LiNi(1/2) Mn(1/2)O(2), standing here as model compounds, during storage and electrochemical cycling. The formation and evolution of the interphase created by decomposition of the electrolyte is investigated by using spectroscopic tools such as magic-angle-spinning nuclear magnetic resonance ((7)Li,(19)F and (31)P) and electron energy loss spectroscopy, in parallel to X-ray photoelectron spectroscopy, to quantitatively describe the interphase and unravel its architecture. The influence of the pristine surface chemistry of the active material is carefully examined. The importance of the chemical history of the surface of the electrode material before any electrochemical cycling and the strong correlation between interface phenomena, the formation/evolution of an interphase, and the electrochemical behavior appear clearly from the use of these combined characterization probes. This approach allows identifying interface aging and failure mechanisms. Different types of surface modifications are then investigated, such as intrinsic modifications upon aging in air or methods based on the use of additives in the electrolyte or carbon coatings on the surface of the active materials. In each case, the species detected on the surface of the materials during storage and cycling are correlated with the electrochemical performance of the modified positive electrodes. PMID:24789623

  16. Nonequilibrium Phase Transformation and Particle Shape Effect in LiFePO4 Materials for Li-Ion Batteries

    SciTech Connect

    Mukherjee, Partha P

    2011-01-01

    The nonequilibrium phase transformation and particle shape effects in LiFePO4 materials of Li-ion batteries are explored in this work. A continuum model employing the mushy-zone (MZ) approach, accounting for sluggish Li diffusion across the two-phase boundary, has been developed to study the kinetically-induced nonequilibrium phenomenon in Li-ion batteries. A theoretical analysis is presented to show that the nonequilibrium miscibility gap expands and shifts to higher Li composition at high discharge rates, due to insufficient compositional readjustments at the two-phase boundary. Furthermore, critical effects of particle shape on nonequilibrium phase transformation and discharge capacity have been discovered by the model.

  17. 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.

  18. 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.

  19. Metal Foam as Positive Electrode Current Collector for LiFePO4-Based Li-Ion Battery

    NASA Astrophysics Data System (ADS)

    Yang, Gui Fu; Song, Jae Sun; Kim, Hyung Yoon; Joo, Seung Ki

    2013-10-01

    In order to improve the kinetic performance of LiFePO4-based Li-ion batteries, three dimensional metal foams were used as positive current collector. In the case of conventional Ni foam, the organic electrolyte of the cell was decomposed with the ionization of Ni during charge and discharge. The low tolerance of Ni was solved by using NiCrAl foam which was manufactured by alloying NiCrAl powder with Ni foam. From the electrochemical analysis, it shows that the kinetic performance of the cell by using a three dimensional NiCrAl foam was much superior to that in the case of conventional foil type.

  20. 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

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

    PubMed

    Saji, Viswanathan S; Song, Hyun-Kon

    2015-01-01

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

  2. Synthesis, characterization and modification of LiFePO4 by doping with platinum and palladium for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Talebi-Esfandarani, Majid

    Lithium iron phosphate (LiFePO4) with features of excellent thermal stability, non-toxicity, low cost and abundance in nature is one of the most promising cathode materials to be used in lithium ion batteries. However, as it suffers from the low electrical conductivity and poor ionic diffusion, it operates only at low charge/discharge current rates. In this thesis, a dual approach of metal doping and carbon coating was employed to solve the aforementioned problem. This work is mainly on the study, for the first time, of the effect of platinum and palladium doping of LiFePO 4 on its physical-chemical properties. The effect of Pt and Pd doping on the LiFePO4 performance as Li-ion cathode will be also shown. Sol-gel and hydrothermal methods were used to synthesize the LiFePO4 and doped-LiFePO4 cathode materials. The prepared materials were characterized using different methods such as XRD (X-ray Diffraction), XPS (X-ray Photoelectron Spectroscopy), SEM (Scanning Electron Microscopy) and BET (Brunauer Emmett Teller). The electrochemical characterization techniques including charge/discharge test, CV (Cyclic Voltammetry), EIS (Electrochemical Impedance Spectroscopy) and cycling were also used. The effects of metals doping on chemical-physical properties, particles sizes, morphology, structure and purity of the electrodes were investigated and their correlation to the electrochemical properties of materials were studied. In the first section, we determine the optimized amount of carbon support and morphology of the particles using SEM which help to obtain LiFePO 4/C cathode material with an excellent electrochemical performance. It was found that when the amount of coated carbon exceeds the optimized value, the discharge capacity of the LiFePO4/C material decreased. This might indicate a low diffusion of the Li+ ions through the carbon layers during the charge/discharge process. On the other hand, for LiFePO4 coated with carbon quantity lower than the optimum value, LiFePO4/C cathode exhibited poor capacity performance due to its low electrical conductivity. Therefore, both the quality and quantity of carbon coating on the surface of LiFePO4 particles are important and only optimized carbon content can lead to a more uniform carbon distribution. Optimized surface area and conductivity, which give high electrochemical performance, can be only achieved if the appropriate carbon content and method of electrode preparation are obtained. In the second part, the effect of doping the LiFePO4/C electrodes with Pt and Pd on the structure, their chemical compositions and electrochemical properties were investigated. The electrodes were prepared using sol-gel method. The chemical composition analysis by XPS of the Pd doped electrodes showed that Pd was detected in the Pd-doped nano composite materials. Also, for Pt doped electrode, Pt was detected in Pt-doped based nano composite materials. Based on the structure and morphology of the non doped and doped electrodes, the results showed that palladium doping facilitated formation of Li 3PO4 impurity in the LiFe0.98Pd0.02PO 4/C and LiFe0.96Pd0.04PO4/C electrodes. Consequently the presence of the Pd in the doped sample reduced the lattice parameters, increased the size of particles and caused their agglomeration. The electrochemical performances of the electrodes showed that their specific capacity decreased when the palladium content increases. Then, the Pd-doped electrodes fabricated using sol-gel method exhibit less discharge capacity than samples of the non-doped LiFePO4/C electrode. The reduction in the level of performance is attributed to several reasons such as the shrinking of the lattice parameters, the formation of Li3PO4 impurity phase, and large particles size. In contrast, for LiFePO4/C doped with Pt using sol-gel method, it was found that the crystallinity and the lattice parameters of LiFe 0.96Pt0.04PO4/C nanocomposite material increased when compared with LiFePO4/C electrode. No impurity was formed in the Pt-doped electrode. In addition, the Pt doped samples exhibited smaller particle sizes (100-200 nm) than the non doped electrode (200-500 nm). More homogeneous and uniform particles were also obtained with LiFe0.96Pt 0.04PO4/C than LiFePO4/C samples. Therefore, platinum doping might provide more space for the diffusion of Li+ ions which facilitates the movement of Li+ ions through the structure of LiFePO4/C material during the redox reactions in the battery, enhancing the discharge capacities. In the third part of this study, LiFe1-xPdxPO 4/C (x = 0.00, 0.02, 0.04) and LiFe0.96Pt0.04PO 4/C nano composite cathode materials were synthesized by a hydrothermal method and the effects of Pd and Pt were examined. The results indicated that the optimized amount of palladium content (0.02%) in the electrode (LiFe 0.98Pd0.02PO4/C) reduced the nano composite particle sizes. This facilitates the Li+ ion diffusion and consequently enhances the reversibility and decreases the charge transfer resistance. The optimized Pd content in the electrode might act as a pillar to prevent the shrinking and collapse of the initial lattice structure. This might support the stabilization of the crystal structure during the intercalation/de-intercalation process of Li+ ions. However, by increasing the palladium content to 4%, the specific capacities decreased due to the Li3PO 4 impurity formation. The presence of such impurity may produce a small surface area for the redox reaction, and causes difficulty of Li+ ion diffusion during the redox electrochemical process. As a result, the optimized palladium doping is helpful in improving the electrochemical performance of LiFePO4/C material. A LiFe0.96Pt0.04PO 4/C based cathode nano material prepared by a hydrothermal method exhibited better performance when compared to the non-doped LiFePO4/C sample. The improvement in the electrochemical performances can be attributed to the combination of the following aspects related to the presence of Pt in the electrode. The platinum element can act as a stabilizing point of the crystal structure during the charge/discharge process. It contributes to the improvement of the redox reaction rate with the increase of the specific surface area of the composite electrode. LiFe0.96Pt0.04PO4/C electrode exhibited homogeneous small particles which might facilitate the Li+ ions diffusion rate. The results show that the chemical and structural properties and electrochemical performances of Pd and Pt doped LiFePO4/C based electrodes to obtain LiFe1-xPdxPO4/C and LiFe1-xPt xPO4/C as Li-ion cathodes are significantly informed by the method of preparation of the materials and the doping element.

  3. LiFePO4 microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G

    PubMed Central

    2014-01-01

    We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed. PMID:24948896

  4. 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%.

  5. 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.

  6. [Laser Raman spectral investigations of the carbon structure of LiFePO4/C cathode material].

    PubMed

    Yang, Chao; Li, Yong-Mei; Zhao, Quan-Feng; Gan, Xiang-Kun; Yao, Yao-Chun

    2013-10-01

    In the present paper, Laser Raman spectral was used to study the carbon structure of LiFePO4/C positive material. The samples were also been characterized by X-ray diffraction (XRD), scanning electron microscope(SEM), selected area electron diffraction (SEAD) and resistivity test. The result indicated that compared with the sp2/sp3 peak area ratios the I(D)/I(G) ratios are not only more evenly but also exhibited some similar rules. However, the studies indicated that there exist differences of I(D)/ I(G) ratios and sp2/sp3 peak area ratios among different points in the same sample. And compared with the samples using citric acid or sucrose as carbon source, the sample which was synthetized with mixed carbon source (mixed by citric acid and sucrose) exhibited higher I(D)/I(G) ratios and sp2/sp3 peak area ratios. Also, by contrast, the differences of I(D)/I(G) ratios and sp2/sp3 peak area ratios among different points in the same sample are less than the single carbon source samples' datas. In the scanning electron microscopy (sem) and transmission electron microscopy (sem) images, we can observed the uneven distributions of carbon coating of the primary particles and the secondary particles, this may be the main reason for not being uniform of difference data in the same sample. The obvious discreteness will affect the normal use of Raman spectroscopy in these tests. PMID:24409720

  7. 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

  8. LiFePO4 microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G.

    PubMed

    Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh

    2014-01-01

    We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed. PMID:24948896

  9. 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.

  10. 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

  11. 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

  12. Understanding the thermal and mechanical stabilities of olivine-type LiMPO4 (M = Fe, Mn) as cathode materials for rechargeable lithium batteries from first principles.

    PubMed

    Xie, Ying; Yu, Hai-Tao; Yi, Ting-Feng; Zhu, Yan-Rong

    2014-03-26

    To elucidate the microscopic origin of the difference behaviors, first-principles calculations were performed to investigate the thermal and mechanical stabilities of LixFePO4 and LixMnPO4. The calculated free energies suggested that LiFePO4 and LiMnPO4 are thermal stable with respect to relevant oxides both in their pristine and fully delithiated states. According to the calculations, it can be identified that the shear deformations are more easier to occur with respect to the volume compressions in LixFePO4 and LixMnPO4, and this phenomenon is related to M-O(I) and M-O(II) bonds. Typically for MnPO4, Li(+) extraction from the host structures further weakens the Mn-O(I) bonds by about 33%, and it thus becomes very brittle. The shear anisotropy (AG) of MnPO4 is abnormally large and has already reached 19.05 %, which is about 6 times as large as that of FePO4. Therefore, shear deformations and dislocations occur easily in MnPO4. Moreover, as the Mn-O(I) bonds in MnPO4 are mainly spread within the {101} and {1̅01} crystal planes, the relevant slip systems thus allow the recombination of bonds at the interfaces, leading to the experimentally observed phase transformation. It can be concluded that mechanical reason will play an important role for the poor cycling performance of MnPO4. PMID:24588772

  13. A novel sol-gel method based on FePO4·2H2O to synthesize submicrometer structured LiFePO4/C cathode material

    NASA Astrophysics Data System (ADS)

    Peng, Wenxiu; Jiao, Lifang; Gao, Haiyan; Qi, Zhan; Wang, Qinghong; Du, Hongmei; Si, Yuchang; Wang, Yijing; Yuan, Huatang

    2011-03-01

    Carbon coated LiFePO4/C cathode material is synthesized with a novel sol-gel method, using cheap FePO4·2H2O as both iron and phosphorus sources and oxalic acid (H2C2O4·2H2O) as both complexant and reductant. In H2C2O4 solution, FePO4·2H2O is very simple to form transparent sols without controlling the pH value. Pure submicrometer structured LiFePO4 crystal is obtained with a particle size ranging from 100 to 500 nm, which is also uniformly coated with a carbon layer, about 2.6 nm in thickness. The as-synthesized LiFePO4/C sample exhibits high initial discharge capacity 160.5 mAh g-1 at 0.1 C rate, with a capacity retention of 98.7% after 50th cycle. The material also shows good high-rate discharge performances, about 106 mAh g-1 at 10 C rate. The improved electrochemical properties of as-synthesized LiFePO4/C are ascribed to its submicrometer scale particles and low electrochemical impedance. The sol-gel method may be of great interest in the practical application of LiFePO4/C cathode material.

  14. 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.

  15. Olivines and olivine coronas in mesosiderites

    NASA Astrophysics Data System (ADS)

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

    1980-08-01

    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.

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. Structural evolution in LiFePO4-based battery materials: In-situ and ex-situ time-of-flight neutron diffraction study

    NASA Astrophysics Data System (ADS)

    Bobrikov, I. A.; Balagurov, A. M.; Hu, Chih-Wei; Lee, Chih-Hao; Chen, Tsan-Yao; Deleg, Sangaa; Balagurov, D. A.

    2014-07-01

    Neutron diffraction has been used for in-situ studying of the charge-discharge processes in commercial lithium batteries with LiFePO4 (LFP) and graphite electrodes. The diffraction data were obtained with time-of-flight diffractometer in the process of three complete charge-discharge cycles performed at a low rate (0.1 C) at room temperature. The experimental data allowed detailed tracing of the multistage process of Li insertion into graphite followed by the formation of several LiCn phases, as well as the reversible transition of LiFePO4 ↔ FePO4. A comparison of the charge-discharge processes in a battery with a pure LFP cathode and LFP containing ˜1% of vanadium (LFPV) is made. In the second case, an evidently larger part of the anode material passes into the final LiC6 state. Analysis of the diffraction patterns of LFP and LFPV powders revealed a marked shrinkage of crystallite size in the LFPV case, which correlates with better electrochemical properties of LFPV compared to LFP.

  2. 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

  3. 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).

  4. 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

  5. Probing the aging effects on nanomechanical properties of a LiFePO4 cathode in a large format prismatic cell

    NASA Astrophysics Data System (ADS)

    Demirocak, Dervis Emre; Bhushan, Bharat

    2015-04-01

    Li-ion batteries offer great promise for the future of energy storage due to their superior gravimetric and volumetric energy density. One of the challenges in promoting their expanded use is to improve the cycle life of Li-ion batteries. This requires detailed understanding of the aging phenomenon. The aging mechanism of Li-ion batteries can have both chemical and mechanical origins. While the chemical degradation mechanisms have been studied extensively, mechanical degradation mechanisms have received little attention so far. In this study, we probe the changes in mechanical properties of a LiFePO4 cathode in a large format prismatic cell. Results indicate that mechanical degradation increases by aging; in addition, local degradation is observed in the composite cathode. Implications of the degradation in mechanical properties on binder degradation are discussed in detail.

  6. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  8. Effects of vanadium substitution on the cycling performance of olivine cathode materials

    NASA Astrophysics Data System (ADS)

    Chen, Mao-Sung; Wu, She-huang; Pang, Wei Kong

    2013-11-01

    V-substituted LiFePO4 (LiFe1-xVxPO4, 0 ≤ x ≤ 0.10) powders are prepared via a solution method. The compositions, crystalline structure, morphology of the prepared powders are systemically investigated with inductive couple plasma-option emission spectrometry (ICP-OES), synchrotron radiation X-ray diffraction (s-XRD), X-ray Absorption Spectroscopy (XAS) and field emission-transmission electron microscopy (FE-TEM). Results of s-XRD and Rietveld analysis reveal that olivine phase is observed exclusively for LiFe1-xVxPO4 (x ≤ 0.05) samples, whereas a minor amount of monoclinic Li3V2(PO4)3 is detected in the prepared LiFe0.93V0.07PO4 and LiFe0.90V0.10PO4 samples. It is also found that the lattice parameters of olivine structure and average Li-O and M-O (M = Fe or V) bond lengths slightly increase and decrease with the amount of V substitution, recommending an enhanced lithium diffusivity in the structure. Results of XAS study suggest that V ions occupy octahedral sites (4c) of Fe in LiFePO4 structure with valence of 3+, showing good agreement with shortened M-O bonds determined in Rietveld analysis. As a result of V substitution, LiFe1-xVxPO4, (0 ≤ x ≤ 0.10) cathodes exhibit better electrochemical performance, such as discharge capacity, rate capability, and cycling performance at both room and elevated temperatures.

  9. 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.

  10. Titanium diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, Daniele J.; Liang, Yan

    2014-12-01

    Diffusion of Ti has been characterized in natural olivine and synthetic forsterite. Experiments on the natural olivines were run under buffered conditions (IW and NNO), and those on synthetic forsterite were run in air. Titanium diffusion appears relatively insensitive to crystallographic orientation and oxygen fugacity under the range of investigated conditions, and diffusivities are similar for Fe-bearing olivine and forsterite. For Ti diffusion in synthetic forsterite, we obtain the following Arrhenius relation for diffusion over the temperature range 900-1400 °C:

  11. 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.

  12. 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.

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

    PubMed

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

    2013-09-25

    A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl2·4H2O as the Fe(2+) source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the LFP micro hollow spheres have a quite uniform size of ~1 μm consisting of aggregated nanoparticles. The influences of solvent and Fe(2+) source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe(2+) ions was firstly proposed on the basis of the X-ray powder diffraction (XRD) transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coat a uniform carbon layer ~3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101, and even 72 mAh g(-1) at 0.1, 1, 5, 20, and 50 C, respectively. It could also maintain 80% of the initial discharge capacity after cycling for 2000 times at 20 C. PMID:23981067

  14. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  16. Thermal modeling of large prismatic LiFePO4/graphite battery. Coupled thermal and heat generation models for characterization and simulation

    NASA Astrophysics Data System (ADS)

    Damay, Nicolas; Forgez, Christophe; Bichat, Marie-Pierre; Friedrich, Guy

    2015-06-01

    This paper deals with the thermal modeling of a large prismatic Li-ion battery (LiFePO4/graphite). A lumped model representing the main thermal phenomena in the cell, in and outside the casing, is hereby proposed. Most of the parameters are determined analytically using physical and geometrical properties. The heat capacity, the internal and the interfacial thermal resistances between the battery and its cooling system are experimentally identified. On the other hand, the heat sources modeling is considered to be one of the most difficult task. In order to overcome this problem, a heat generation model is included. More specifically, the electrical losses are computed thanks to an electrical model which is represented by an equivalent electric circuit. A method is also proposed for parameter determination which is based on a quasi-steady state assumption. It also takes into account the battery heating during characterization which is the temperature variation due to heat generation during current pulses. This temperature variation is estimated thanks to the coupled thermal and heat generation models. The electrical parameters are determined as function of state of charge (SoC), temperature and current. Finally, the proposed coupled models are experimentally validated with a precision of 1 C.

  17. 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.

  18. 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

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

    PubMed

    Assat, Gaurav; Manthiram, Arumugam

    2015-10-19

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

  20. 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.

  1. Exogenous Olivine on Vesta

    NASA Astrophysics Data System (ADS)

    Hoffmann, Martin; Nathues, Andreas; Schäfer, Michael; Thangjam, Guneshwar; Le Corre, Lucille; Vishnu, Reddy; 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

    2014-11-01

    Vesta has conserved an early status of planetary evolution, demonstrated by the global coverage of HED lithology on its surface. Being sufficiently large to retain some material from slow projectiles, but small enough to prevent its complete evaporation during the impacts, this unique environment is ideal for distinction and identification of exogenous material. In particular, the distribution, concentration, and geological context of olivine exposures are poorly consistent with a Vestan mantle origin. Similar arguments are valid for the areas of dark carbonaceous chondrite-like lithology, and a few other features with unusual visual spectral slopes. Most olivine is found close to the large impact craters Bellicia, Arruntia, and Pomponia in the northern hemisphere, whose ejecta sheet is characterized by a mixing trend from an HED lithology to S- or A-type asteroid material. The olivine has diagnostic significance for the extent and duration of differentiation during the early accretion of parent bodies in the asteroid region. Sources for exogenous olivine are available in Vesta’s environment among A- and S-type asteroids. It is not clear, however, if it is derived mainly from achondritic or chondritic sources. On the other hand, the lack of evidence for Vesta’s mantle material implies constraints on its inner structure, e.g. the depth of the crust.

  2. "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.

  3. 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.

  4. 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

  5. A new method to synthesize olivine phosphate nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, D. H.; Kim, T. R.; Im, J. S.; Kang, J. W.; Kim, J.

    2007-12-01

    Well-crystalline LiFePO4 nanoparticles were prepared by the polyol process without post heat treatments. X-ray diffraction showed an orthorhombic phase without any discernible existence of impurities. The particles showed highly crystalline nature of rod and plate like morphologies with an average size of 300 nm. The initial discharge curve of LiFePO4 showed a capacity of 168 mAh g-1 at a 0.1 C rate in the voltage range of 2.5-4 V with good retention at high rate current densities. This amounts to a utilization efficiency of 98%, with excellent reversibility in extended cycles. LiFePO4 nano-particle showed a high capacity of 102 mAh g-1 at a high rate of 6.4 C.

  6. 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.

  7. Structural, magnetic, and energetic properties of Na2FePO4F, Li2FePO4F, NaFePO4F, and LiFePO4F from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Ramzan, M.; Lebègue, S.; Larsson, P.; Ahuja, R.

    2009-08-01

    In this paper, we report on Na2FePO4F and Li2FePO4F, which are materials that are used as cathodes in batteries, using density functional theory with the LDA, LDA+U, GGA, or GGA+U approximations. Specifically, we study their crystal structure, electronic structure, and magnetic properties and provide similar information about the intermediate compounds LiFePO4F and NaFePO4F. Finally, the intercalation voltages of the corresponding batteries are calculated using various exchange-correlation approximations and conclusions are drawn about which one is the most suitable to use for the study of this class of materials.

  8. Defects in Microwave Solvothermally Grown Phospho-Olivine Nanoparticles

    SciTech Connect

    Bridges, Craig A; Harrison, Katharine L; Unocic, Raymond R; Idrobo Tapia, Juan C; Paranthaman, Mariappan Parans; Manthiram, Arumugam

    2013-01-01

    Microwave solvothermally (MW-ST) synthesized crystalline nanopowders of LiFePO4 have been structurally characterized using a combination of high resolution powder neutron diffraction, synchrotron X-ray diffraction and HAADF STEM images. The presence of a significant level of defects has been verified for the samples prepared at 255 oC and 275 oC. These temperatures are significantly higher than what has previously been suggested to be the maximum temperature for defect formation in LiFePO4, and their presence likely relates to the rapid synthesis provided by the MW-ST approach. 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.

  9. 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

  10. 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.

  11. 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.

  12. Supernova olivine from cometary dust.

    PubMed

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

    2005-07-29

    An interplanetary dust particle contains a submicrometer crystalline silicate aggregate of probable supernova origin. The grain has a pronounced enrichment in 18O/16O (13 times the solar value) and depletions in 17O/16O (one-third solar) and 29Si/28Si (<0.8 times solar), indicative of formation from a type II supernova. The aggregate contains olivine (forsterite 83) grains <100 nanometers in size, with microstructures that are consistent with minimal thermal alteration. This unusually iron-rich olivine grain could have formed by equilibrium condensation from cooling supernova ejecta if several different nucleosynthetic zones mixed in the proper proportions. The supernova grain is also partially encased in nitrogen-15-rich organic matter that likely formed in a presolar cold molecular cloud. PMID:15994379

  13. Supernova olivine from cometary dust

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

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

  14. 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

  15. 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.

  16. 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 absence of decompression cracks within olivine overgrowths suggests depths <25 km. Late stage (<25 km) resurfacing and reshaping of olivine by particle-particle milling is indicative of turbulent flow conditions within a fully fluidized, gas-charged, crystal-rich magma.

  17. 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.

  18. 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.

  19. 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.

  20. 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 connections between the olivine-dominated asteroids and asteroid families found no genetic link (of the type core-mantel-crust) between these objects.

  1. 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.

  2. 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.

  3. 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/.

  4. Exsolved Ferromagnesian Olivine: Why Only in Divnoe?

    NASA Astrophysics Data System (ADS)

    Petaev, M. I.

    1995-09-01

    Recently Petaev and Brearley [1] showed that lamellar structure in olivine grains in the Divnoe meteorite was produced by the low-temperature exsolution of primary homogeneous grains. Exsolved olivine in Divnoe is in accordance with the thermodynamic model of olivine solid solution of [2], which predicts a miscibility gap in ferromagnesian olivines below ~340 degrees C within a compositional range that widens with decreasing temperature. Experiments on the coexistence of olivines having a range of compositions with aqueous solutions of (Fe,Mg)Cl2 [3] suggest that exsolution in ferromagnesian olivines could occur even at temperatures as high as ~400 - 450 degrees C. However, [1] remains the only observation of exsolution in natural olivines so far. This means either that (1) the exsolution in Divnoe olivine is unique, or (2) olivine grains in other slowly cooled coarse-grained rocks has not been studied closely enough to detect them. This work attempts to clarify the issue. Olivine grains from selected meteorites (Springwater pallasite, Lowitz mesosiderite, ALHA 84025 brachinite, Gorlovka H3-4 chondrite and Krymka L3 chondrite, and the Calcalong Creek lunar meteorite) and terrestrial rocks (San Carlos forsterite and Rockport fayalite) were studied by EPMA using the same equipment and technique as in [1]. Among meteorites, pallasites and mesosiderites are known to have slowest cooling rates at low temperatures. Olivines in the Springwater pallasite (Fa18) [4] and the Lowitz mesosiderite (Fa15-37) [5] are compositionally comparable with that of Divnoe (Fa23-29) [1], and it was expected that exsolved olivine grains would be found there. Olivines from other samples were studied for comparison. No lamellar structure was observed in BSE images of the olivine grains studied. The variations of Fa contents in olivine grains from all samples but Springwater and Lowitz meteorites display no regular pattern, and are basically within the 2sigma uncertainty range (+/-0.2 mole % Fa). As expected, olivines from the Lowitz mesosiderite and, especially, from the Springwater pallasite display somewhat larger variations, within the ranges of 20.1 - 21.0 and 15.8 -17.7 mole % Fa, respectively. The olivine in Springwater shows a surprisingly regular pattern of minima spaced at ~ 16 micrometers. For reasons that are unclear all 'minima' analyses have low totals (90.47-94.31 wt.%), whereas most other analyses have totals > 97%. However, stoichiometry of all analyses is perfect; cation totals per 4 oxygens are 3.00+/-0.01, with very minor excess of Si over Mg+Fe in the 'minima' analyses. The results obtained so far suggest that lamellar structure of olivine grains in the Divnoe meteorite is unique. While chemical variability is found in the Springwater and Lowitz olivines, there is no lamellar structure, and the magnitude of the variations is 1.5 - 2 times smaller than it is in Divnoe olivines. Since olivine compositions in Divnoe, Lowitz and Springwater are similar, the structural differences among them must be due to different thermal histories. The lack of lamellar structure in the Lowitz olivine implies that even the slowest cooling down to 250 degrees C recorded in mesosiderites [6] does not result in olivine exsolution. It is possible that Divnoe experienced secondary reheating followed by prolonged low-temperature annealing. This would also account for the lack of shock features in the Divnoe opaque minerals [7] and the difference in distributions of cosmic-ray track lengths and densities between olivine and pyroxene [8]. References: [1] Petaev M. I. and Brearley A. J. (1994) Science, 266, 1545-1547. [2] Sack R. O. and Ghiorso M. S. (1989) Contrib. Mineral. Petrol., 102, 41-68. [3] Schulien S. (1980) Contrib. Mineral. Petrol., 74, 85-91. [4] Buseck P. R. (1977) GCA, 41, 711-740. [5] Delaney J. S. et al. (1980) Proc. LPSC 11th, 1073-1087. [6] Ganguly J. et al. (1994) GCA, 58, 2711-2723. [7] Petaev M. I. et al. (1994) Meteoritics, 29, 182-199. [8] Petaev M. I. et al. (1990) LPS XXI, 950-951.

  5. An experimental investigation of olivine morphology

    NASA Technical Reports Server (NTRS)

    Donaldson, C. H.

    1976-01-01

    Results are reported for a morphological study of olivine and an experimental investigation performed to determine the degrees of supercooling and the cooling rates necessary to crystallize particular morphologies. Ten arbitrary categories of three-dimensional olivine crystal shape are identified: polyhedral, granular, hopper, chain, lattice, plate, branching, radiate, feather, and swallow-tail. The morphological study establishes that equant and tabular crystals are the common shapes of olivine, nonequant crystals are elongate parallel to the a or c axis, and skeletal crystals result when a particular form is missing or only partially developed. In the experiment, olivine crystals were grown by melting rock samples above their liquidus temperatures before initiating crystallization. The results show that olivine morphology changes systematically as a function of the degree of melt supercooling, the melt cooling rate, and the normative olivine and water contents of the melt. It is also found that each shape has a specific range of temperature stability which is essentially independent of melt composition.

  6. Atom Probe Tomography of Olivine

    NASA Astrophysics Data System (ADS)

    Parman, S. W.; Gorman, B.; Jackson, C.; Cooper, R. F.; Jaeger, D.

    2010-12-01

    Here we present atom probe tomographic (APT) analyses of natural olivine. APT provides three-dimensional trace element and isotopic analysis with sub-nanometer spatial resolution. It has been used for many years in engineering and materials science, but has not been applied to geological materials because traditional APT can only be used on conducting (usually metal) samples. The recent development of laser assisted APT has changed this situation, and now semi-conductors and insulators can be analyzed (Marquis et al., 2009, Kelly et al 2007). Potentially, this opens APT to extensive use in geoscience as many Fe-bearing silicates are semi-conductors. In this study, we explore the capability of the new class of APT instrumentation to analyze geological materials. APT involves the controlled evaporation of small, cylindrical specimens (100's nm in diameter) within an electric field. Specimens are typically prepared using in-situ focused-ion-beam (FIB) liftout and shaping techniques. Evaporated atoms are accelerated to a detector plate that records the position of the atom with sub-nm precision. Evaporated atoms are measured using time-of-flight mass spectrometry, allowing both elemental and isotopic determination. Since the method progressively ablates into the needle, the final analytical result is a nm-scale 3-dimensional image in which the position and identity of each detected atom is known. Typical mass resolution is between 200 and 1200 (full-width at half maximum) and typical concentration detection limits are 10 ppm. The number of potential applications of APT to igneous, metamorphic and sedimentary materials is large, ranging from studies of mineral and melt inclusions, to fine scale layering in minerals, to reaction surfaces and diffusion profiles. Much recent progress in the geochemical and petrologic fields has been driven by the increasing spatial resolution of the ion probe and laser ablation ICPMS. The ability of APT to provide atom-scale mass spectrometry should continue this trend. The main limitations to atom probe analysis of geological materials are the ability to control heat flow during laser pulsing and the associated ability to control clustering during field evaporation. Both of these factors can be controlled through specimen preparation and varying the atom probe experimental factors. Olivine specimens were properly analyzed using laser pulsed APT through the use of shallow (nominally 1mm) FIB liftouts and wide shank angle specimen apices. APT settings were found to give the best mass resolution using low specimen temperatures, 0.2 nJ laser energy, and 50 kHz pulse repetition rate. Increasing any of these values increases the amount of thermal tails due to excessive heat buildup, reducing the mass spectrum resolution, and ultimately affecting the spatial resolution of the reconstruction. Marquis EA, Miller MK, Blavette D, Ringer SP, Sudbrack CK and Smith DW (2009). MRS Bulletin 34: 725-730. Thomas F. Kelly, David J. Larson, Keith Thompson, Roger L. Alvis, Joseph H. Bunton, Jesse D. Olson, Brian P. Gorman, Ann. Rev. Mat. Res. 37: 681-727.

  7. Amoeboid olivine aggregates in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Grossman, L.; Steele, I. M.

    1976-01-01

    Greyish-brown irregularly-shaped aggregates composed predominantly of olivine make up nearly 2% of the Allende meteorite by volume. Many of the aggregates are constructed of subspherical lumps of micron-sized crystals of olivine, pyroxene, nepheline and sodalite surrounded by coarser-grained olivine. Rarely, anorthite, spinel and perovskite are also present. The olivine ranges in composition from Fo64 to Fo99. Pyroxenes range from aluminous diopside to hedenbergite to very Al-rich and Ti-Al-rich varieties. The nepheline contains 1.6-2.4% K2O and 1.6-5.2% CaO but the sodalite is significantly poorer in these elements. The spinel contains 2.1-13.4% FeO. Textural information and oxygen isotopic data suggest that the aggregates are composed of primary, solid condensates from the solar nebula. The perovskite, spinel and Ti-Al-rich pyroxenes are the remains of high-temperature condensates, but the olivine compositions and the presence of feldspathoids indicate that some of the grains continued to react with the solar nebular vapor in the temperature range 500-900 K.

  8. 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.

  9. 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.

  10. 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.

  11. A Chemical Model of Micrometeorite Impact into Olivine

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

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

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

    USGS Publications Warehouse

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

    1990-01-01

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

  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. Evaluation of olivine refractories for TES

    NASA Astrophysics Data System (ADS)

    Gay, B. M.; Cochrane, R. L.; Palmour, H., III; Paisley, M. J.

    1982-02-01

    The principal objectives of this program are to (1) experimentally determine the degree of improvement in thermal and mechanical performance that can be obtained with an olivine thermal storage brick made of domestic materials using advanced processing techniques compared with state-of-the-art as represented by commercial European bricks, (2) conduct an assessment of existing German ceramic process technology and determine its adaptability to domestic raw materials and manufacturing practices, and (3) investigate, on a limited basis, method for further improvement of domestic-olivine brick. To date, accomplishments include (1) installation of improved, computer-based instrumentation, (2) the use of this system to determine performance characteristics of a set of heat storage refractories under cyclic use conditions, (3) acquisition of the services of a knowledgeable European consultant, (4) continued lab-scale process/property optimization studies, and (5) comparative testing of olivine-based and magnesite-based heat storage refractories in the calorimetric test facility at Purdue University.

  15. 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 potential sources of olivine on Vesta could be different types of olivine-rich meteorites, either primitive achondrites (acapulcoites, lodranites, ureilites), ordinary chondrites (H, L, LL), pallasites, or carbonaceous chondrites (e.g., CV). Based on our spectral band parameters analysis, the lack of correlation between the location of these olivine-rich terrains and possible mantle-excavating events, and supported by observations of HED meteorites, we propose that a probable source for the olivine seen in the northern hemisphere corresponds to remnants of impactors made of olivine-rich meteorites. The best curve-matching results with laboratory spectra suggest these units are HED material mixed with either ordinary chondrites, or with some olivine-dominated meteorites such as R-chondrites.

  16. 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.

  17. Effect of Olivine Alteration on Seismic Velocities in Oceanic Gabbros

    NASA Astrophysics Data System (ADS)

    Carlson, R. L.; Newman, J.; Miller, D. J.

    2006-12-01

    Seismic velocities in oceanic gabbros are expected to increase with increasing olivine content, but this relationship is has not been observed in gabbros recovered by drilling, and inverse methods yield elastic moduli that are anomalously low. Two hypotheses have been advanced to explain these observations: one is that the olivine grains in these rocks may contain a high concentration of cracks that affect their elastic moduli, and the other is that the olivines in the gabbros have lower Mg numbers (median Fo73) and hence lower moduli than olivines that are typical of upper mantle rocks (~Fo90). Our SEM analyses of gabbro samples show that cracks in the olivine grains are sealed by serpentine; because they are sealed in situ, cracks cannot explain the low moduli. The elastic moduli of Fo73 are higher than effective moduli of olivine in the samples. However, though very little alteration of olivine to serpentine was reported in the modal analyses of these rocks, our SEM analysis of gabbros from ODP Hole 923A shows significant alteration of olivine to serpentine and magnetite. To explore the effect of this alteration on the relationship between seismic velocities and modal mineral content, we have used the known properties of olivine (Fo73), serpentine, magnetite, plagioclase, pyroxene and amphibole to match VRH model velocities to measured velocities by adjusting the degree of alteration of olivine in the gabbro samples from Hole 923A. We assume that the alteration products are 95% serpentine and 5% magnetite. Our analysis of the 25 samples from Hole923A indicates that an average of 10-30% alteration of Fo73 to serpentine and magnetite is sufficient to explain the low elastic moduli, and suggest that the lack of correlation between seismic velocities and olivine contents arises from variable alteration that is not correlated with initial olivine content.

  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 and their mixtures.

  19. 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 diffusion occurs on both a metal and interstitial site and that lithium is able to jump between these two sites. The best fits to the results show that diffusive isotopic fractionation may occur on both the interstitial and metal site but the degree of diffusive isotopic fractionation is always greater on the interstitial site.

  20. 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.

  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. 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.

  3. 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.

  4. Olivine in an unexpected location on Vesta's surface.

    PubMed

    Ammannito, E; De Sanctis, M C; Palomba, E; Longobardo, A; Mittlefehldt, D W; McSween, H Y; Marchi, S; Capria, M T; Capaccioni, F; Frigeri, A; Pieters, C M; Ruesch, O; Tosi, F; Zambon, F; Carraro, F; Fonte, S; Hiesinger, H; Magni, G; McFadden, L A; Raymond, C A; Russell, C T; Sunshine, J M

    2013-12-01

    Olivine is a major component of the mantle of differentiated bodies, including Earth. Howardite, eucrite and diogenite (HED) meteorites represent regolith, basaltic-crust, lower-crust and possibly ultramafic-mantle samples of asteroid Vesta, which is the lone surviving, large, differentiated, basaltic rocky protoplanet in the Solar System. Only a few of these meteorites, the orthopyroxene-rich diogenites, contain olivine, typically with a concentration of less than 25 per cent by volume. Olivine was tentatively identified on Vesta, on the basis of spectral and colour data, but other observations did not confirm its presence. Here we report that olivine is indeed present locally on Vesta's surface but that, unexpectedly, it has not been found within the deep, south-pole basins, which are thought to be excavated mantle rocks. Instead, it occurs as near-surface materials in the northern hemisphere. Unlike the meteorites, the olivine-rich (more than 50 per cent by volume) material is not associated with diogenite but seems to be mixed with howardite, the most common surface material. Olivine is exposed in crater walls and in ejecta scattered diffusely over a broad area. The size of the olivine exposures and the absence of associated diogenite favour a mantle source, but the exposures are located far from the deep impact basins. The amount and distribution of observed olivine-rich material suggest a complex evolutionary history for Vesta. PMID:24196707

  5. 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.

  6. 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 deposits and map the geology, composition and stratigraphy of surface features. The instrument will also watch the seasonal variations in Martian dust and ice aerosols, and water content in surface materials -- leading to new understanding of the climate.

    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.

  7. Chemical dispersion among Apollo 15 olivine-normative mare basalts

    NASA Technical Reports Server (NTRS)

    Ryder, Graham; Steele, Alison

    1988-01-01

    Analysis of Apollo 15 olivine-normative mare basalts for major and minor elements suggests that the hypothesis that the coarser-grained varieties (olivine microgabbros) consist of two chemical groups is incorrect. Instead, it is found that there is a single group including vesicular, coarse-grained, and fine-grained basalts. For the entire suite, the dispersion of compositions along the olivine trend is too great to be explained by short-range unmixing of an unfractionated flow. It is suggested that the general trend for the suite is olivine separation, probably through crystal settling. The textures, mineralogical characteristics, and chemical variation of the olivine-normative basalts are shown to be consistent with a sequence of thin fractionating flows, all from a common parent.

  8. 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.

  9. 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.

  10. The pattern of Ni and Co abundances in lunar olivines

    NASA Astrophysics Data System (ADS)

    Longhi, John; Durand, Sedelia R.; Walker, David

    2010-01-01

    Near liquidus experiments on peridotite and other olivine normative compositions from 1.7 to 6 GPa confirm the applicability of exchange-based empirical models of Ni and Co partitioning between olivine and silicate liquids with compositions close to the liquidus of peridotite. Given that most estimates of lunar bulk composition are peridotitic, the partitioning models thus lend themselves to calculation of olivine compositions produced during the early stages of magma ocean crystallization. Calculation of olivine compositions produced by fractional crystallization of a model lunar magma ocean, initially 700 km deep, reveals a prominent maximum in Ni concentration versus fraction crystallized or Mg' (molar MgO/(MgO + FeO)), but a pattern of monotonically increasing Co concentration. These patterns qualitatively match the puzzling patterns of Ni and Co concentrations observed in lunar rocks in which forsteritic olivines in magnesian suite cumulates have lower Ni and Co abundances than do less magnesian olivines from low-Ti mare basalts, and olivines from the ferroan anorthosite suite (FAS) have lower Ni, but similar Co to mare basalt olivines. The Ni and Co abundances in olivines from the magnesian suite cumulates can be reconciled in terms of fractional crystallization of a deep magma ocean which initially produces a basal dunite comprised of the hottest and most magnesian olivine overlain by an olivine-orthopyroxene (harzburgite) layer that is in turn overlain by an upper zone of plagioclase-bearing cumulates. The ultramafic portion of the cumulate pile overturns sending the denser harzburgite layer, which later becomes a portion of the green glass source region, to the bottom of the cumulate pile with Ni- and Co-rich olivine. Meanwhile, the less dense, but hottest, most magnesian olivines with much lower Ni and Co abundances are transported upward to the base of the plagioclase-bearing cumulates where subsequent heat transfer leads to melting of mixtures of primary dunite, norite, and gabbronorite with KREEP (a K-REE-P enriched component widely believed to be derived from the very latest stage magma ocean liquid). These hybrid melts have Al 2O 3, Ni, and Co abundances and Mg' appropriate for parent magmas of the magnesian suite. Ni and Co abundances in the FAS are consistent with either direct crystallization from the magma ocean or crystallization of melts of primary dunite-norite mixtures without KREEP.

  11. 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.

  12. 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 overgrowths mainly originating from dissolved orthopyroxene, showing enrichment in Zr, Ga, Nb, Sc, V, P, Al, Ti, Cr, Ca and Mn in the melt trend. In a sample of magmatic kimberlite from the Leslie pipe, the amount of xenocrystic and phenocrystic olivine is estimated to be around 23 vol.% and 19 vol.%, respectively. Subtraction of this xenocrystic olivine from the Leslie bulk composition, aimed at estimating the parental kimberlite melt, results in a minor decrease of Mg# (by about 0.01) and SiO2 content (by about 3 wt.%), whereas CaO increases (by about 3 wt.%).

  13. 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.

  14. 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 detections. An alternative and very recent option can be represented by the model according to which surface "eruption" of material from the mantle, including olivine can reach the surface of Vesta.

  15. 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.

  16. Olivine Deposits Associated with Impact Basins and Craters on Mars

    NASA Astrophysics Data System (ADS)

    Ody, A.; Poulet, F.; Langevin, Y.; Gondet, B.; Bibring, J.; Carter, J.

    2011-12-01

    An analysis of the 1?m olivine spectral signature applied to the entire and final OMEGA dataset [1] shows numerous olivine-bearing deposits in the 3 main basins of Mars (Argyre, Isidis and Hellas). These signatures are among the strongest of Mars, which suggests compositions with higher iron content and/or larger grain size and/or larger abundance than the ones of widespread olivine-bearing deposits observed on large parts of the southern highlands [1]. A spectral modeling based on a radiative transfer model [2] indicates that their compositions are still close to the forsterite one with abundance in the range of [15,40%] and grain sizes of a few hundreds of ?m. These deposits are exclusively localized on Noachian terrains. Distribution of these deposits around Argyre basin clearly takes the form of discontinuous patches of olivine-bearing rocks on the basin terrace, which strongly suggest that their formation is related to the basin formation event. Recent numerical simulations of basin formation show that impact that formed the Argyre basin could have excavated upper mantle materials and emplaced discontinuous patches of melted mantle on the basin terraces [3]. The observed olivine deposits in Argyre are thus interpreted as olivine-bearing material excavated from the upper mantle during the impact. Olivine deposits distribution around the Hellas basin is not as clear as for Argyre because of young resurfacing processes that strongly affected its region. Olivine deposits are fewer and mainly localized on the northern terrace of Hellas. Most of them are detected in crater ejecta, while a few similar to Argyre olivine discontinuous patches are also observed suggesting that a mantle origin as for Argyre is possible. Olivine has been detected by several datasets in the Nili Fossae region and in the south of Isidis basin. The spectral modeling of OMEGA spectra indicates an olivine abundance of about 40% and megacrysts of several millimeters for the region of Nili Fossae [2]. Several plausible hypotheses has been discussed to explain this unusual concentration of olivine-rich outcrops in Nili Fossae assuming three possibilities for their emplacement relative to the formation of the Isidis basin : pre-impact [4,5], contemporaneous [6], or post-impact [7]. The pretty unique settings and compositions of these deposits in comparison to the two other major basins indicate a different origin, with the post-impact one as the preferred one. Other several localized exposures with strong olivine signature are also found throughout the southern highlands and the northern plains mostly associated with craters. Olivine-bearing material is found in craters floors but also in some crater ejecta implying the presence of an olivine-rich underlying layer. Of special interest are some craters totally filled by olivine-rich lava lakes, which could have erupted through local (impact-related) fractures. [1] A. Ody et al. (2011) LPSC XXXXII.[2] F. Poulet et al. (2009), Icarus 201, 84-101.[3] Stewart S. (2010) AGU, San Francisco, abstract #P43A-08. [4] Hoefen et al. (2003) Science,302,627-630.[5] Hamilton and Christensen (2005), Geology,33,433-436.[6]J.F. Mustard et al. (2007), JGR, 112, E08S03.[7] L.L Tornabene et al. (2008), JGR, 113, E10001.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Materials Data on LiMnPO4 (SG:62) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-11-02

    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

  2. Detection of new olivine-rich locations on Vesta

    NASA Astrophysics Data System (ADS)

    Palomba, E.; Longobardo, A.; De Sanctis, M.; Tosi, F.; Capria, M.; Capaccioni, F.; Ammannito, E.; Raymond, C.; Russell, C.

    2014-07-01

    The recent discovery of olivines on Vesta by the VIR imaging spectrometer onboard the Dawn space mission changed dramatically the vision about the Vestan petrogenetic models [1]. Before that, olivines were expected to be present in the Vesta interior: in the mantle of a vertically layered body as invoked by the magma ocean models [2] or at the base of (or within) the mantle-crust boundary as claimed by fractionation models [3]. Olivines were detected by VIR-Dawn in two wide areas near the Arruntia and Bellicia regions. These are located in the northern hemisphere and not in the south, where the Rheasilvia and the more ancient Veneneia huge basins should have excavated the crust down to reach the mantle. In this work, we present our attempts to retrieve 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 [4,5]). As a preliminary step, we calibrated these parameters by means of VIS-IR spectra of different HED meteorite samples: their behaviors as a function of sample grain size and albedo were retrieved and discussed. We selected the BAR and the forsterite index as the best parameters that can be used on Vesta and applied two independent methods to detect olivine signatures on the VIR hyperspectral cubes: a cross-correlation and an anti-correlation analysis between the BAR and one of the olivine parameters. In agreement with the recent discovery, Arruntia and Bellicia were the most olivine rich areas. In addition, we detected 6 new regions, all but one located in Vesta's northern hemisphere. This result confirms again that the old petrogenetic models cannot be applied, in a straightforward way, to Vesta and should be reshaped in the view of these new detections. An alternative and very recent option can be represented by the model described in [4], in which surface ''eruption'' of material from the mantle, including olivine, can reach the surface of Vesta.

  3. 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 200C and 300C, 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 has to be further investigated but this result motivates a re-evaluation of the natural rates of olivine serpentinization and of olivine hydrolysis in general in a wide range of settings where olivines or peridotites are intimately associated with Al-providers. Such a fast reaction rate may affect the contribution of reaction-enhanced processes at the micrometer-scale, such as reaction-driven cracking, already proposed for enhancing serpentinization or carbonation of olivine. The effect of Al on lower crust and upper mantle metasomatism is expected to be even stronger at higher pressure in subduction zones where those reactions control the rheology and physical properties of the subducting plate and mantle wedge.

  4. 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.

  5. Microstructures of Olivine in the Weakly Shocked Divnoe Meteorite

    NASA Astrophysics Data System (ADS)

    Ando, J.; Tomioka, N.; Petaev, M. L.; Kanagawa, K.; Honda, K.; Shibata, Y.; Yamanaka, S.

    2003-12-01

    Many microstructural observations of minerals in meteorites show evidences of shock effect, but rarely give data about the parent body. However, the microstructures of minerals in achondrites may retain the important information about the parent body which gives a basic idea about the formation of internal structural of the Earth. We carried out microstructural and microfabric analyses of olivine grains in the Divnoe meteorite by optical microscopy, electron probe microanalysis, electron back-scattered diffraction (EBSD) analysis, and transmission electron microscopy (TEM) with the selected area electron diffraction, in order to search the microstructures produced in the parent body. The Divnoe meteorite is a granoblastic, olivine-rich primitive achondrite. Neither black shock veins nor pockets of silicate melt typical of heavily shocked meteorites were found. Most olivine grains exhibit weak undulose extinction. Some grains show mosaic extinction though this is not as pronounced as in heavily shocked meteorites, and lamellar Fe-Mg zoning (2 to 4 mole percent Fa). The weak shock metamorphism experienced by Divnoe is consistent with the shock stage S3. The EBSD analysis of the Divnoe olivine grains reveals a distinct crystallographic preferred orientation (CPO) characterized by a [001] density maximum and girdle distributions of [100] and [010] around the [001] maximum. This type of fabric is not known in crystal-plastically deformed Earths mantle rocks, and can be explained by rigid body rotation of olivines in matrix flow. It suggests that this CPO was formed by rotation of olivine grains in strong melt flows on the meteorite parent bodies, so that their longest [001] axes were aligned parallel to the flow direction. Therefore, Divnoe should preserve an initial CPO of olivine formed during crystallization in the parent body that has not been significantly disturbed by later processes such as thermal and shock metamorphism. Now, the microstructures such as dislocations and inclusions within the single crystal olivines showing the CPO which should retain the important information about the parent body are examining by TEM.

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

    NASA Technical Reports Server (NTRS)

    Witteborn, F. C.; Roush, T. L.; Cohen, M.

    1999-01-01

    Thermal emission spectra of the largest asteroid 1 Ceres obtained from the Kuiper Airborne Observatory display features that may provide information on its surface mineralogy. A plot of the Ceres spectrum (calibrated using alpha Boo as a standard) divided by a standard thermal model (STM) is shown. Also shown is the emissivity spectrum deduced from reflectivity measurements for olivine grains <5 microns in diameter. The general shape of the Ceres and the olivine curves agree in essential details, such as the maxima from 8 to 12 microns, the minimum between 12 and 14 microns, the broad peak near 17.5 micron, and the slope beyond 22 micron. (Use of the 10 to 15-micron grain reflectivities provides a better match to the 12- to 14-micron dip. We used a value of unity for beta, the beaming factor associated with small-scale surface roughness in our STM. Adjustment of beta to a lower value raises the long-wavelength side of the Ceres spectrum, providing an even better match to the olivine curve.) The emissivity behavior roughly matches the emission coefficients which were calculated for olivine particles with a particle radius of 3 microns. Their calculations show not only the negative slope from 23 to 25 pm, but a continued decrease past 30 micron. The Ceres emissivity is thus similar to that of small olivine grains from 8 to 30 micron, but olivine's emissivity is lower from 5 to 8 pm.

  7. 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. Grain boundary diffusion perpendicular to the dislocation lines of the small angle grain boundaries proved to be about an order of magnitude faster than volume diffusion, whereas diffusion in high angle grain boundaries is several orders of magnitude faster. We will discuss the variation of element diffusion rates with grain boundary orientation and the temperature- and/or time-induced transition from one diffusion regime to the next regime. This is done using time series experiments and two-dimensional grain boundary diffusion simulations. Finally, we will debate the differences between our data and other data sets that result from different experimental setups, conditions and analyses.

  8. 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 quartz (SiO2) powder in a 1:1:1 ratio. The advantage of using siderite is that the iron is already present in the ferrous form. Upon heating and decarbonation, this mixture represents a bulk composition of Fo50 (FeMgSiO4) olivine. Flux was then added to the starting material mixture so that the final mixture was 50% starting material and 50% flux by weight. This final mix was then placed in a platinum crucible that was heated to 1100 °C in a vacuum furnace for three days. The use of a vacuum furnace ensured that conditions remained reducing during crystal growth. The result was growth of olivine crystals that are generally small (< 1 mm in length) and have euhedral crystal form. These crystals have been analyzed by electron microprobe, and are systematically zoned from core to rim with Mg-rich cores (˜Fo70) transitioning to Fe-rich rims (˜Fo30). This zoning represents an expected heterogeneity due to olivine growth from a finite reservoir of starting material. The flux growth of this intermediate composition olivine was primarily a 'proof of concept' experiment, and showed that olivine crystals can be grown using a flux under sub-solidus conditions. Additional crystal growth experiments would be useful to gauge the response of olivine to changes in temperature, duration, and composition of the flux + starting material mixture.

  9. Formation of a metastable olivine wedge in a descending slab

    SciTech Connect

    Devaux, J.P.; Schubert, G.; Anderson, C.

    1997-11-01

    We present a thermal model of a descending slab in which the transformation of olivine to spinel is controlled by pressure- and temperature-dependent reaction kinetics. Two different formulations of the kinetics are considered with the main discriminant being the temperature range over which olivine converts to spinel at pressures of about 15 GPa (about 500{degree}{endash}515{degree}C and 560{degree}{endash}650{degree}C). We use a finite element method to solve the coupled heat conduction (perpendicular and parallel to the dip of the slab) and kinetics equations, and we include the latent heat of the phase transformation. Latent heat release together with heat conduction parallel to the dip of the slab reduces significantly the length of the metastable olivine wedge and results in a very thin ({approx_lt}5km) two-phase region. We employ the thermal parameter v{tau}sin{delta} (v is the velocity of the descending slab, {tau} is the age of the slab, and {delta} is the dip of the slab to the horizontal) to interpret the results for the length of the metastable wedge. For values of the thermal parameter smaller than about 4000 and 7000 km, depending on the model of the kinetics, no metastable olivine wedge exists (the critical value of 7000 km for the thermal parameter corresponds to the kinetics model with the lowest transition temperature range). The length of the metastable olivine wedge is also found to be very sensitive to the model of the kinetics and to the effects of adiabatic heating. If the occurrence of deep earthquakes is related to the transformation of metastable olivine to spinel, then data on earthquake depth versus thermal parameter require that the onset of the reaction takes place at temperatures of about 550{degree}{endash}575{degree}C. In this case the slab thermal parameter must be larger than 10,000 km for the metastable olivine wedge to extend down to 660 km depth. But deep earthquakes occur near 660 km depth in slabs with thermal parameter as small as about 5000 km (South America, for example). Either some deep earthquakes are unrelated to olivine metastability or our knowledge of olivine-spinel reaction kinetics is incomplete.{copyright} 1997 American Geophysical Union

  10. 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 Board of Regents on behalf of the University of Arizona.

  11. 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.%.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  13. 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.

  14. 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.

  15. 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 pressure vessel (Brown University). The starting materials were prepared by cutting gem-quality San Carlos olivine (~Fo90) into small blocks (~4×2×1 mm) using a diamond wafering blade saw and polishing with alumina slurries and colloidal silica. Analysis was completed by laser ablation-mass spectrometry using a 193 nm excimer laser and a MAP 215-50 specifically tuned for He (Open University, UK). Laser ablation pit depth varied from 2 to 40 μm, and no correlation between pit depth and [He] is observed after accounting for variations PHe across the different experiments. This lack of correlation indicates a close approach to equilibrium was achieved over the experimental durations. Two analyses yielded spuriously high [He] (>3 std. dev. from the population mean, n = 85), and these analyses were not used to calculate Henry's coefficients. The two spuriously high analyses, in combination with the right skew of Henry's coefficients calculated from individual data points, suggests gem-quality San Carlos olivine contains volumes with anomalously high helium solubility. The nature of these volumes is currently under investigation. However, despite their presence, helium is still highly incompatible in olivine during partial melting. [1] Lux GCA 1987 [2] Heber et al. GCA 2007 [3] Shcheka & Keppler Nature 2012 [4] Walker et al. PEPI 2009

  16. 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.

  17. 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.

  18. 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., Jutzi, M., Barrat, J.-A., Gillet, Ph. [2014]. Lunar Planet Sci. 45, #1349; Jutzi, M., Asphaug, E., Gillet, P., Barrat, J.-A., Benz, W. [2013]. Nature 494, 207-210), which predict an excavation depth of up to 80 km, we are confident that the crust-mantle depth is significantly deeper than predicted by most evolution models (30 km; Mittlefehldt, D.W. [2014]. Asteroid 4 Vesta: A Fully Differentiated Dwarf Planet. NASA Technical Reports Server (20140004857.pdf)) or, alternatively, the olivine-content of the (upper) mantle is lower than our detection limit, which would lead to the conclusion that Vesta's parent material was already depleted in olivine compared to CI meteorites.

  19. 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

  20. Thermal Emission Spectroscopy of 1 Ceres: Evidence For Olivine

    NASA Astrophysics Data System (ADS)

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

    2000-03-01

    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 μm size range). The smoothness of the spectrum beyond 18 μm is an indication of particles smaller than 50 μm. While the abrupt rise in emissivity near 8 μm matches many silicates, the distinct emissivity minimum centered near 12.8 μm 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.

  1. 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 hibonite in CAIs within AOAs reflects heterogeneous distribution of 26Al in the solar nebula during this epoch. The observed variations of the inferred initial 26Al/27Al ratios in anorthite of the mineralogically pristine and uniformly 16O-rich CH AOAs could have recorded (i) admixing of 26Al in the protoplanetary disk during the earliest stages of its evolution and/or (ii) closed-system Mg-isotope exchange between anorthite and Mg-rich minerals (spinel, forsterite, and Al-diopside) during subsequent prolonged (days-to-weeks) thermal annealing at high temperature (∼1100 °C) and slow cooling rates (∼0.01 K h-1) that has not affected their O-isotope systematics. The proposed thermal annealing may have occurred in an impact-generated plume invoked for the origin of non-porphyritic magnesian chondrules and Fe,Ni-metal grains in CH and CB carbonaceous chondrites about 5 Myr after formation of CV CAIs.

  2. A Survey of Olivine Alteration Products Using Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

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

    2004-01-01

    Identification of mineral alteration products will aid in the crucial task of interpreting past Martian environmental conditions, especially aqueous environments. Olivine has been identified at the surface of Mars and is readily altered in aqueous environments. Using Raman spectroscopy, we studied three rocks with altered olivine and compared the data with mineral chemistry from electron microprobe analysis. Although the alteration in all three samples has loosely been called iddingsite their appearances and modes of occurrences differ as described. Alteration products in all three samples are likely fine-grained mixtures.

  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.

    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.

  4. Global investigation of olivine on Mars: Insights into crust and mantle compositions

    NASA Astrophysics Data System (ADS)

    Ody, A.; Poulet, F.; Bibring, J.-P.; Loizeau, D.; Carter, J.; Gondet, B.; Langevin, Y.

    2013-02-01

    present the distribution of olivine on Mars, derived from spectral parameters based on the 1 µm olivine absorption band. The olivine can be defined with respect to two spectral end-members: type 1 corresponds to olivine with low iron content and/or small grain size and/or small abundance, and type 2, which corresponds to olivine with higher iron content and/or larger grain size and/or larger abundance. The spatial and statistical analysis of the global olivine distribution points out five major geological settings where olivine is detected: (1) Early Hesperian olivine-bearing smooth crater floors and flat intercrater plains throughout the southern highlands; (2) olivine deposits around the three main basins Argyre, Hellas, and Isidis; (3) olivine in intercrater dunes, crater ejecta, or extended deposits in the northern plains; (4) olivine associated with outcrops and sand in the floor of Valles Marineris; and (5) olivine-bearing butte outcrops in the vicinity of Hellas. The geological context, the age, and the composition of the olivine detections associated with these five major geological settings are detailed. Their origin and the implication of their occurrence on the composition of the Martian mantle and crust, as well as on the evolution of Mars volcanism are discussed.

  5. 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 fractionation on a single, initially homogeneous parent asteroid. For Al and Ti, the low and high Mn/Mg clusters have generally uniform contents, while the medium cluster has wide ranges. This is also true of analyses of duplicate grains from the medium cluster pallasites which can have very different Al and Ti contents. Those from the low and high clusters do not. These observations suggest that pallasite olivines are not cumulates, but rather are restites from high degrees of melting. The moderately siderophile elements P and Ga show wide ranges in the high Mn/Mg cluster, but very uniform compositions in the medium cluster, opposite the case for Al and Ti. There is no correlation of P or Ga and Fe/Mn as might be expected if redox processes controlled the contents of moderately siderophile elements in the olivines. The lack of correlation of P could reflect equilibration with phosphates, although there is no correlation of Ca with P as might be expected

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    The reactivity of ultramafic rocks under hydrothermal conditions controls chemical fluxes at the interface between the internal and external reservoirs of silicate planets. On Earth, hydration of ultramafic rocks is ubiquitous and operates from deep subduction zones to shallow lithospheric environments where it considerably affects the physical and chemical properties of rocks and can interact with the biosphere. This process also has key emerging societal implications, such as the production of hydrogen as a source of carbon-free energy. To date, the chemical model systems used to reproduce olivine hydrothermal alteration lead to the formation of serpentine with sluggish reaction rates. Although aluminum is common in geological environments and in hydrothermal systems in particular, its role in serpentinization or olivine dissolution has not been investigated under hydrothermal conditions. Nevertheless, abundant Al supply is expected in fluids released from dehydration of metapelites in subduction zones as well as during the hydrothermal alteration of gabbros at mid-ocean ridges. Aluminum was also abundant in primitive environments of both the Earth and Mars, stored in either Al-rich minerals like plagioclase or Al-enriched ultramafic lavas. We have investigated the role of Al on the hydrothermal alteration of olivine in a series of experiments performed in a low-pressure diamond anvil cell while following the reaction progress in situ by optical imaging and by confocal Raman spectroscopy. Experiments were run for 4.5 to 7.5 days with two olivine grains reacted in saline water (0.5 molal NaCl) at 200C and 300C, and P=200 MPa. After two days, olivine crystals were fully transformed to an aluminous serpentine, also enriched in iron. The very fast precipitation of serpentine may inhibit magnetite nucleation here. However, this does not rule out an H2 production since serpentines classically incorporate non negligible amount of ferric iron in their structure. The presence of Al in the hydrothermal fluid increases the rate of olivine serpentinization by more than one order of magnitude by increasing olivine solubility and enhancing serpentine precipitation. The mechanism responsible for this increased solubility has to be investigated further but this result motivates a re-evaluation of the natural rates of olivine serpentinization and of olivine hydrolysis in general in a wide range of settings where olivines or peridotites are intimately associated with Al-providers. Such a fast reaction rate may affect the contribution of reaction-enhanced processes at the micrometer-scale, such as reaction-driven cracking, already proposed for enhancing serpentinization or carbonation of olivine. The effect of Al on lower crust and upper mantle metasomatism is expected to be even stronger at higher pressure in subduction zones where those reactions control the rheology and physical properties of the subducting plate and mantle wedge. Finally, this study also provides a way to accelerate serpentinization reactions towards economically feasible time-scale and temperature for industrial H2 production and/or CO2 remediation.

  7. Chemical zonation in olivine-hosted melt inclusions

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    Significant zonation in major, minor, trace, and volatile elements has been documented in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (e.g., MgO, FeO, Cr2O3, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H2O, and F, components with a lower concentration in the host olivine than in the melt (e.g., Al2O3, SiO2, Na2O, K2O, TiO2, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions, concurrent with diffusive propagation of the boundary layer toward the inclusion center. Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na2O, K2O) by coupling to slow diffusing components such as SiO2 and Al2O3. Concentrations of H2O and F decrease toward the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects. A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150-13,000 C h-1 from the liquidus down to ~1,000 C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1,000 C ranges from 40 s to just over 1 h. Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization. All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

  8. 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.

  9. Far-infrared continuum absorption of olivine at low temperatures

    NASA Astrophysics Data System (ADS)

    Mutschke, H.; Zeidler, S.; Chihara, H.

    2013-10-01

    The far-infrared continuum opacity of cold dust is an important quantity for the study of debris disks in planetary systems and of protoplanetary disks. Olivine is considered the most abundant crystalline dust species in such environments. We present spectroscopic absorption measurements on olivine plates of the order of a millimeter thickness at wavelengths between 60 and 400 μ m for temperatures down to 10 K. Our data reveal a strong temperature dependence of the continuum absorption coefficient, i.e. more than an order of magnitude decrease at 100 μ m for 10 K compared to room temperature. The absolute values are generally much lower than those measured with olivine powders embedded into polyethylene pellets, even if the difference between plate and powder samples is taken into account by theoretical models. In contrast to this, the room temperature data are in relatively good agreement with simulations using optical constants determined from reflection measurements. At low temperatures, the absorption coefficient of olivine was measurable with sufficient accuracy only up to 90 μ m for 10 K and up to 110 μ m for 100 K. These data reveal a drastic change in the spectral slope (from β ~ 2.0 to β > 5.0) for the continuum underlying the 69-μ m band, which is not predicted by the low-temperature optical constants determined for forsterite.

  10. 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.

  11. The search for exsolved ferromagnesian olivines: A meteoritic survey

    NASA Astrophysics Data System (ADS)

    Petaev, Michail I.

    1996-11-01

    Olivine grains from selected meteorites (the Springwater pallasite, the Lowicz mesosiderite, the ALH 84025 brachinite, the Krymka LL3 chondrite, and the Calcalong Creek lunar meteorite) and terrestrial rocks (San Carlos forsterite and Rockport fayalite) were studied by optical microscopy and high-precision electron microprobe analysis. Detailed microprobe traverses revealed regular igneous zoning in the Krymka and Calcalong Creek olivines. Traverses across the San Carlos forsterite grain are flat and display no chemical variations larger than the 2? range of counting error (0.2 mol% Fa). Traverses across olivine grains in the ALH 84025, Lowicz, and Springwater meteorites show regular patterns of periodic or wavy chemical variations well exceeding the 2? uncertainty range. However, no lamellar structure was seen in backscattered electron images. It is suggested that the periodic chemical variations may be due to spinodal decomposition of primary, more or less homogeneous grains. I conclude that the absence of earlier reports of such variations simply means that olivine grains in equilibrated meteorites have not been examined closely enough to detect them.

  12. 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.

  13. The effect of mineral paragenesis on Al diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Zhukova, Irina; O'Neill, Hugh; Capbell, Ian

    2014-05-01

    Al is the most abundant trivalent impurity of olivine and is particularly important because its concentration in olivine is temperature dependant, and it therefore has potential as a geothermometer (Wan, et al. 2008). Furthermore recent studies show that the incorporation of water into the olivine lattice is affected by the presents of trivalent cations such as Al3+ (Berry, et al. 2007; Hauri, et al. 2006). The Al distribution in olivines from volcanic rocks is often zoned and mantle olivines may also show an inhomogeneous distribution of Al, whereas the majority of other trace elements homogenized by diffusion (Mallmann, et al. 2009; McKibbin, et al.). However, there are no quantitative experimental data for Al diffusion in olivine, probably because the combination of low concentration rate and low diffusion rate make measurement difficult. We investigated the effect of silica activity on the diffusion rate of Al in forsterite at varying temperatures using solid-state buffer assemblages. Our study aimed to quantify the effect of major cation activities on the diffusion and concentration of Al in forsterite and also provide insights into the mechanism of Al substitution into the olivine lattice. The activities of SiO2, MgO and Al2O3 were buffered in each experiment by four different mineral associations: forsterite + periclase + spinel (fo+per+sp); forsterite + spinel + sapphirine (fo+sp+spr); forsterite + sapphirine + cordierite (fo+spr+cor); forsterite + cordierite + enstatite (fo+cor+en). Iron oxide in proportion of FeO/(FeO+MgO) = 0.1 was added to mixtures for San Carlos olivine experiments. Diffusion experiments were performed at the one-atmosphere vertical tube furnaces modified to control the fO2 by CO-CO2 gas mixing or in a box furnace in air for 10 - 28 days at temperatures from 1100 to 1500oC and logfO2 -0.7 and -5.7. The experiment with the San Carlos olivine was performed at 1300oC and at logfO2 = -5.7. In order to obtain equilibrium concentrations of the point defects we performed some experiments with pre-annealing. Diffusion profiles were measured by LA-ICP-MS in a traverse mode. The Al content of forsterite decreases with temperature dependence, increasing the potential of Al in olivine as a geothermometer. We obtain the activation energy of 379 kJ/mol for the high aSiO2 experiments, which is close within error of the value of 364 kJ/mol for the low aSiO2 experiments implying a common diffusion mechanism. The pre-exponential factor, however, increases by 5 orders of magnitude from low aSiO2 (fo+per+sp buffer) to high aSiO2 (fo+cor+en buffer). The much higher diffusivity at high aSiO2 indicates that Al diffusion occurs through octahedral cation site vacancies.

  14. 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

  15. 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.

  16. Olivine as a key to unlocking Kilauea's magmatic history

    NASA Astrophysics Data System (ADS)

    Garcia, M. O.; Norman, M. D.

    2011-12-01

    Olivine is a ubiquitous mineral in Hawaiian basalts. It is on the liquidus at pressures <0.5 GPa and has the potential to record numerous petrologic processes including the histories of parental magma composition changes, crystal fractionation, magma mixing and crustal contamination. These processes are recorded in olivine composition (major and trace elements, and isotopes) and by melt inclusions trapped within olivine. Here we focus on Kilauea's historical lavas (1820-present) to evaluate the magmatic history one of world's most active volcanoes. Kilauea has shown dramatic variations in it eruptive rate and style (from vigorous, quiescent effusion in 1820 to infrequent explosive activity in 1924 and then to its highest effusion during the last decade). Eruption rates correlate with whole-rock compositional and isotopic variations (P-G 1999). Most Kilauea lavas have normally zoned olivine in equilibrium with whole-rock compositions which belies complex magma chamber processes. Parental magma composition changed rapidly based on the heterogeneity of melt inclusion compositions in higher Mg olivine (>86 forsterite). Melt inclusions from single eruptions show wider variation in ratios of Ca/Al and Nb/Y than observed in lavas for the historical period. Thus, the mantle source is heterogeneous on a small scale and small batches of compositionally distinct melt are frequently delivered to the volcano. These magma batches undergo mixing, fractionation and after caldera collapses (e.g.1924), crustal contamination in the summit reservoir. This work demonstrates that an Ernstonian approach, using minerals to understand petrologic processes, is key to unlocking Kilauea's magmatic processes. Pietruszka, A.P. and Garcia, M.O., 1999, J. Petrol. 40, 1321-1342.

  17. Exsolution of ferromagnesian olivine in the Divnoe meteorite

    NASA Astrophysics Data System (ADS)

    Petaev, M. I.; Brearley, A. J.

    1994-07-01

    The Divnoe meteorite is a granoblastic olivine-rich primitive achondrite whose textural and mineralogical characteristics suggest extensive recrystallization during slow cooling in the temperature range from approximately 1000 to approximately 500 C and lower. Olivine grains in this meteorite show a lamellar appearance in BSE images, caused by minor micrometer-scale chemical variations in Fe, Mg, and Mn contents between adjacent lamellae. Ten grains of lamellar olivine were studied in detail by Electron Probe Microanalysis (EPMA) and optical microscopy and two of these by Transmission Electron Microscopy (TEM). The olivine grains studied are essentially free of minor elements (Ti, Al, Cr, Ni, Ca, Na) except for Mn, and fall in the compositional range found by an earlier study. While the compositional ranges of Fe-poor and Fe-rich lamellae overlap, the differences between lamellae richest and poorest in Fe are quite similar, suggestive of their formation by an equilibrium process. Fine-scale microprobing has confirmed earlier compositional data, but has reduced lamella thicknesses to a few micrometers, which is in a good agreement with TEM observations. The structural and compositional data obtained strongly suggest that the lamellar structure in these olivine grains was produced by an exsolution process, which is in qualitative agreement with a recent thermodynamic analysis of phrase relations in the system Mg2SiO4-FeSiO2. Cracks in Fe-rich lamellae could result from expansion during the exsolution process due to the volume difference between Fe-rich and Fe-poor lamellae.

  18. The geoengineering potential of artificially enhanced silicate weathering of olivine

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

    Geoengineering is a proposed action to manipulate Earth's climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate in more detail 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, because it influences the global climate via the carbon cycle. We here show the consequences of this technique for the chemistry of the surface ocean at rates necessary for geoengineering. We calculate that olivine dissolution has the potential to sequestrate up to one Pg C yr-1 directly, if olivine is distributed as fine powder over land areas of the humid tropics. The carbon sequestration potential 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 C yr-1. 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 to 5 Pg C yr-1 for the 21st century by this technique. At maximum this technique would reduce global warming by 1 K and counteract ocean acidification by a rise in surface ocean pH by 0.1 in the year 2100.

  19. 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.

  20. 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 obtained at high pressure, i.e., it translates into a high activation volume V*>14 cm3/mol for [100](010) and a low V*<9 cm3/mol for [001](010)in both Fo100 and Fe-bearing olivine. We also show that the combined activity of [100](001) and [001](100) systems translates into V*=12± 3 cm3/mol, suggesting that pressure also reduces both system activities. All together, our data show that olivine [001](010) system dominates deformation at the mantle P and T.

  1. 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 the (100)ol is parallel to the (001)atg or the (010)ol is parallel to the (001)atg. And, the a[100] axes of olivine are normal to serpentinite foliation with point maximum in the thin section scale. However, in the case of this study, the simple topotactic relationship does not connect the fabric in the thin section scale of serpentinite schist. Although, more detail analysis need to discuss the formation of antigorite LPO, the other mechanisms, such as crystal plastic deformation or diffusion-precipitation, might cause rearrangement of antigorite fabric. References Bezacier, L. et al., 2010, Earth and Planetary Science Letters, 289, 198-208. Boudier, F. et al., 2010, Journal of Petrology 51, 495-512. Hirauchi et al., 2010, Earth and Planetary Science Letters, 299, 196-206. Jung, H., 2011, Earth and Planetary Science Letters, 307, 535-543. Katayama, I., et al., 2009, Nature, 461, 1114-1118. Soda, Y. and Takagi, H., 2010, Journal of Structural Geology, 32, 792-802.

  2. 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.

  3. 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.

  4. Evidences and consequences of slow hydrogen diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Padron-Navarta, J. A.; Hermann, J.; O'Neill, H. S.

    2014-12-01

    In the most abundant upper mantle phase, olivine, the presence of hydrogen significantly modifies the timescale of chemical diffusion, plastic deformation, electrical conductivity and the attenuation of seismic waves. Early experiments showed that hydrogen is the fastest species able to diffuse through the olivine lattice. We have found, however, experimental and natural evidence suggesting that hydrogen diffusion can also be orders of magnitude slower. In olivine there are four different hydrogen substitution mechanisms, associated with Mg vacancies, Si vacancies, trivalent cations and titanium substitution, hereafter referred to as H[Mg], H[Si], H[triv] and H[Ti] respectively. We experimentally investigated the dehydroxylation of synthetic forsterite with two contrasting hydrous defect populations: (1) dominated by H[Si], and H[Ti] with subsidiary H[Mg] and H[triv]; and (2) H[Si] exclusively. The loss rates of H[Mg] and H[triv] are in agreement with previous measurements of bulk hydrogen diffusion in forsterite, but the decrease in H[Ti] and H[Si] are ~1.5 and ~ 3 orders of magnitude slower, respectively. The activation energy and pre-exponential terms derived in these experiments are in agreement with the empirical correlation recently proposed based on the Meyer-Nedel compensation law (Jones 2014, G3, 15, 2616-2631). Natural observations attest further to slow hydrogen diffusivity in olivine dominated by H[Ti] and H[Si]. Metamorphic olivines formed after dehydration reactions in the Alpine orogeny preserve their original water contents despite long times of exhumation (2-3 Ma). Closure temperature calculations suggest that using previous fast diffusion rates, these olivines should reequilibrate down to 400C. Only slow hydrogen diffusion coefficients such as those corresponding to H[Si] are able to explain the observed preservation of water content at the peak metamorphic temperature (700-800C). These findings have implications for estimating the ascent rate of xenoliths, which are more consistent with other independent constrains, as recently noted (Hilchie et al. 2014, Lithos, 202-203, 429-441). They are also required to assess the time necessary to equilibrate experimental charges, since for the different hydrous defects this time would vary by orders of magnitudes.

  5. 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 incipient cracks were observed, providing clear evidence that these cracks are generated by isotropic tensile stresses. This strongly indicates that the observed cracking was caused by volume expansion during mineral carbonation. The experimental results provide a mechanism for near 100% alteration of ultramafic rocks observed in nature.

  6. 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

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

    PubMed

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

    2015-01-20

    Olivine-type lithium manganese phosphate (LiMnPO4) has been considered as a promising cathode for next-generation Li-ion batteries. Preparation of high-performance LiMnPO4 still remains a great challenge because of its intrinsically low Li-ion/electronic conductivity. In this work, significant performance enhancement of LiMnPO4 has been realized by a controllable acid-engaged morphology tailoring from large spindles into small plates. We find that acidity plays a critical role in altering the morphology of the LiMnPO4 crystals. We also find that size decrease and plate-like morphology are beneficial for the performance improvement of LiMnPO4. Among the plate-like samples, the one with the smallest size shows the best electrochemical performance. After carbon coating, it can deliver high discharge capacities of 104.0 mAh g(-1) at 10 C and 85.0 mAh g(-1) at 20 C. After 200 cycles at 1 C, it can still maintain a high discharge capacity of 106.4 mAh g(-1), showing attractive applications in high-power and high-energy Li-ion batteries. PMID:25559416

  8. 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.

  9. 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.

  10. H defects in forsterite and olivine: A critical review

    NASA Astrophysics Data System (ADS)

    Ingrin, J.

    2012-12-01

    The current state of knowledge of hydrogen defects in olivine, highlighted by the recent results of numerical modelling, infrared measurements and experiments is presented. In laboratory's experiments, two types of defects control the solubility of water at high pressure: a defect associated with silicon vacancies and a defect of unknown origin identified in infrared by a single OH band at 3555 cm-1. At low pressure and in natural samples, the dominant defects are linked to Ti4+ and trivalent substitutions and more occasionally to defects associated to Si vacancies, Mg vacancies or even the unknown defect at 3555 cm-1. Mosenfelder et al. (2006) [1] already pointed out the difference of incorporation mechanisms between low and high-pressure experiments. We speculate on the impact of different defects on the solubility laws of hydrogen in olivine and their consequences for mantle solubility. [1] Mosenfelder et al. (2006) Amer. Min., 91, 285-294.

  11. 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.

  12. Experimental study of Mg isotope fractionation during olivine dissolution

    NASA Astrophysics Data System (ADS)

    Qiu, L.; Wang, Z.

    2012-12-01

    The dissolution of silicate minerals plays important roles in modifying the chemical composition of the ocean and earth crust. Previous studies show secondary clay minerals produced as a by-product of dissolution are enriched in heavy Mg isotopes compared with their protolith. In this study, batch olivine dissolution experiments were conducted in an autoclave to understand the evolution of Mg isotope composition in the solution as a function of controlled experimental conditions, including initial pH of the fluid (10.02 or 2.02), temperature (50, 100, or 200oC), olivine-grain size (<30μm powder or single olivine grain of ~0.2g/each), and duration of the experiments (up to ~60 hours). At the end of experiments, solid minerals were characterized by SEM and EM, and the solution was analyzed for major and trace element, and Mg isotope compositions by Element-XR and Neptune at Yale University. The Mg/Si ratio of the solution and the SEM and EM characterization of the solid phases indicate the formation of secondary mineral-talc in experiments with alkaline solutions, is consistent with the calculated saturation index. Significant Mg isotope fractionations were also observed in these experiments, which decrease with increasing temperature (e.g., up to ~ -5.8‰ at 50oC vs. -0.72 ‰ at 200oC), but increase with increasing the duration of the experiments. In contrast, little fractionation was observed in experiments with acidic solutions at low temperatures, or short duration of the experiments at high temperatures. These results indicate that dissolution of olivine (even in our closed system experiments) is a surface controlled process, during which Mg isotopes fractionate insignificantly, whereas secondary minerals formed during the process are strongly enriched in heavy Mg isotopes, leaving the solutions depleted in 26Mg. The fractionation factors between solution and talc have been estimated for these experiments as well.

  13. 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.

  14. 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 crystallography, but with time Fe-metal blebs are randomly distributed throughout the olivine. In a given experiment, dusty olivine can be found in varying stages of development, but in the longest experiments, the Fe-metal blebs are dominant and they appear to be migrating out of the olivine. The composition of the dusty olivine ranges from Fo 94-99. The Cr, Mn, and Ca content of the newly formed, dusty olivine is slightly less on average that the precursor olivine, but is till with the range of type 1 olivine. Chadacrysts in the low Ca pyroxene are most common in the higher temperature, more slowly cooled experiments and range in composition from Fo 90-99. Application to chondrule formation: These experiments place time-temperature limits on the preservation of Fe-rich olivine and the production of dusty olivine during chondrule forming events. The reduction process proceeds in a few hours at temperatures above 1400 C and in 10's of hours at temperature between 1200 and 1300 C. This result further confirms th at chondrules form in a few hours to days as suggested earlier. The experiments also confirm that dusty olivine can form from typical Fe-rich olivine in UOC material during the recycling of such olivine in the chondrule forming process.

  15. 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

  16. Experimental deformation of olivine single crystals at lithospheric temperatures

    NASA Astrophysics Data System (ADS)

    Demouchy, Sylvie; Schneider, Stephen E.; Mackwell, Stephen J.; Zimmerman, Mark E.; Kohlstedt, David L.

    2009-02-01

    Rheological properties of mantle minerals and rocks at temperatures (T) appropriate to much of Earth's lithosphere have remained poorly constrained, even though past experimental studies on olivine single crystals and polycrystalline aggregates have quantified the high-temperature creep mechanisms (T > 1200°C). Consequently, we have performed deformation experiments on crystals of San Carlos olivine at lower temperatures, from 900° to 1200°C, in triaxial compression along the [101]c direction. The experiments were carried out at a confining pressure of 300 MPa in a high-resolution gas-medium mechanical testing apparatus at differential stresses of 100 to 500 MPa. Several samples were deformed at constant displacement rate and others at constant load, in order to provide insight into possible effects of work-hardening. Under the deformation conditions investigated, little evidence of work-hardening was observed. The data follow a power-law dependence on stress, as in previous high-temperature deformation studies. The samples were, however, considerably weaker than predicted by the experimentally determined high-temperature constitutive equation for olivine crystals of this orientation from the study of Bai et al. (1991). The mechanical behavior correlates instead with the weaker of the two mechanisms (flow laws) that contribute to the high-temperature constitutive equation. Thus, our experiments demonstrate that published high-temperature constitutive equations overestimate the strength of lithospheric mantle and that the transition to low-temperature creep occurs at lower temperatures than previously inferred.

  17. New measurements of activation volume in olivine under anhydrous conditions

    NASA Astrophysics Data System (ADS)

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

    2009-01-01

    A new cell assembly for the deformation-DIA (D-DIA) shows promise for limiting the water content of samples and providing a more mechanically stable environment for deformation. The 6-mm cubic cell consists of a 6-mm diameter mullite sphere cradled in a web of unfired pyrophyllite. The pyrophyllite flows during initial compression of the D-DIA to form gaskets between the six anvils while the mullite flows to become a nearly cubic-shaped pressure medium. Measurements on olivine indicate more than one order of magnitude drop in water content to <40 ppm H/Si compared with the boron-epoxy medium. Improved mechanical stability is achieved by elimination of the thermocouple from the assembly and determination of temperature from calibration curves of furnace power vs. temperature. Three samples of polycrystalline orthopyroxene-buffer San Carlos olivine have been deformed in high-temperature creep in the new cell, at pressures of 2.7-4.9 GPa and temperatures near 1473 K. Strength is consistent with that measured in the gas-apparatus at lower pressures. Over the pressure range investigated we resolve an activation volume for creep of dry olivine of V* = 9.5 ± 7 × 10 -6 m 3/mol.

  18. Olivine-rich asteroids in the main asteroid belt

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  19. 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.

  20. Origin of plagioclase-olivine inclusions in carbonaceous chondrites

    SciTech Connect

    Sheng, Y.J.; Hutcheon, I.D.; Wasserburg, G.J. )

    1991-02-01

    Plagioclase-Olivine Inclusions (POIs) are an abundant group of chondrule-like objects with igneous textures found in carbonaceous chondrites. POIs consist of plagioclase, olivine, pyroxene, and spinel, and cover a wide range of compositions between Type C Ca-Al-rich Inclusions (CAIs) and ferromagnesian chondrules. POIs are distinguished from CAIs by the absence of melilite, lack of refractory siderophile-rich opaque assemblages, more sodic plagioclase, and abundance of olivine and aluminousenstatite. Rare accessory minerals including armalcolite, zirconolite, rutile, and sapphirine are found in several POIs. The petrographic and chemical properties of POIs indicate that they are not condensates or evaporative residues but formed by melting or partial melting of pre-existing solids. Seven of fourteen POIs contain isotopically fractionated Mg, and despite their textures these POIs are not isotopically homogeneous. A comparison of the essential characteristics of POIs and CAIs suggests that the major processes leading to formation of POIs - including condensation, dust/gas fractionation, aggregation of chemically and isotopically disparate materials, and partial melting - are common to most CAIs and chondrules. We present a scenario for the formulation of these objects and conclude that the homogeneity of the final assemblage - CAI, POI, or chondrule - is primarily a reflection of the thermal history rather than the nature of precursor materials.

  1. Ontogenetic analysis of individual olivine grains in ultramafic rocks

    NASA Astrophysics Data System (ADS)

    Brodskaya, R. L.; Bilskaya, I. V.; Markovsky, B. A.

    2010-12-01

    The morphology and internal structure of individual olivine grains from ultramafic rocks in the Guli and Gal'moenan dunite massifs differing in origin are considered. To restore the ontogeny of mineral aggregates, traces of elastic deformation retained in mineral grains have been used. Comparison of anatomy of olivine grains from these two massifs showed that the mechanism of accommodation of rocks to changing geological settings is expressed as the response of the mineral aggregate structure and variation in the anatomy of individual mineral grains. At the level of individual grains, this is annihilation of older defects and origination of younger dislocations; refinement of the crystal lattice; exsolution; formation and transformation of new mineral phases; and creep and migration of subboundaries within grains. At the aggregate level, this is rotation and migration creep of the internal boundaries of rock; formation of new boundaries of mineral intergrowths; reorientation of boundaries; and variation in their extent, density, and grain dimensions. The prehistory of massifs controls the manifestation and abundance of various elastic deformations and related types of recrystallization of olivine grain boundaries and subboundaries in aggregates. New conditions and accommodation of mineral aggregates to these conditions have instigated specific schemes of recrystallization, which bear information on the history of rocks and their massifs.

  2. Value enhancement of olivine process dust through air classification

    NASA Astrophysics Data System (ADS)

    Kleiv, R. A.

    2012-03-01

    As a result of the production of dry olivine sand products at A/S Olivin's production plant at Åheim in western Norway, an annual quantity of some 20000-30000 t of process dust is produced. The bulk of this material is currently being sold as a slag conditioner at a relatively low price; hence, alternative uses of the process dust are now being sought. Information regarding the chemical composition of the material as a function of particle size facilitates product modifications through exclusion or mixing of individual size fractions. This paper demonstrates how such information can be obtained from air classification experiments when these are combined with chemical analysis of the produced size fractions. The classification and subsequent analysis of the olivine process dust revealed that the finer size fractions had high loss on ignition (LOI) values and were relatively low in MgO when compared with the bulk analysis. Removal of the finer fractions resulted in a remaining coarse product of significantly higher quality. The coarse material could be used as a raw material for further processing; it could be recycled or it could constitute a new product in itself.

  3. In Situ Investigation of Preirradiated Olivines in CM Chondrites

    NASA Astrophysics Data System (ADS)

    Metzler, K.

    1993-07-01

    Most CM chondrites are breccias that contain fragments of primary rock representing densely packed agglomerates of chondrules, CAIs, etc., all of which are mantled by thick layers of fine-grained mineral dust [1]. These dust mantles seem to be the result of dust sampling by the various components during their isolated existence in the solar nebula prior to the formation of the CM parent body [1]. Metzler et al. [1] concluded that these rock fragments are well-preserved remnants of the freshly accreted CM parent body(ies). There is an opposing hypothesis that favors an origin of the dust mantles in an active regolith on the CM parent body [e.g., 2]. A list of arguments against the latter view is given by Metzler et al. [1], including a hint at the absence of solar-wind-implanted gases in dust mantles and in fragments of primary rock. In analogy to brecciated ordinary chondrites and lunar breccias, the most probable residence of the solar gases in CM chondrites is their clastic matrix. The same holds for track-rich olivines that were observed in CM chondrites. The occurrence of these grains in the clastic matrix and their absence in the primary rock would give an additional argument for the idea of a dust mantle origin in the solar nebula rather than in a planetary regolith. To answer this important question, mosaics of backscattered electron images of several large polished thin sections of Murchison and Cold Bokkeveld were prepared. The thin sections (1.5-5 cm^2 each) were etched in a WN solution [3] for about 4 hr to reveal the heavy ion tracks in olivines. Results: The background GCR track density produced during meteoroid transit is on the order of 10^4 tracks/cm^2, as was previously observed by [4]. Following the definition given by Goswami and Lal [4], olivines with track densities >10^5 tracks/cm^2 were classified as preirradiated grains and were found in both meteorites in a very small quantity. In both meteorites, 39 preirradiated isolated olivine grains were found in the clastic matrix, whereas the investigated fragments of primary rock do not contain preirradiated olivines. In Murchison about 1.8% (15 out of 850 investigated grains) of the isolated olivines in the clastic matrix show high track densities in the range between 1.9 x 10^6 and >5 x 10^7, comparable to the results of Goswami and co-workers [4,5]. Both Fe-poor and Fe-rich olivines with grain sizes between 40 and 710 micrometers were found to be preirradiated. Track gradients were found in 33% of these olivines, which is very similar to the values obtained by Goswami and Lal [4] and identical to those obtained by MacDougall and Phinney [6]. About 0.4% (2 out of 530) of the investigated olivine-bearing chondrules and chondrule fragments are preirradiated. In the case of Cold Bokkeveld, 3.7% (24 out of 650) of the isolated olivines show high track densities. Thirteen of these 24 grains were found to be concentrated in a distinct inclusion (1 x 4 mm) that is characterized by its elongated appearence and clastic fabric. The track densities of its preirradiated olivines show a very narrow range, indicating a common irradiation history of these grains. The petrography of this inclusion is currently under investigation. Conclusions: Track-rich (preirradiated) olivines in CM chondrites occur exclusively in the clastic matrix of these meteorites, comparable to observations in brecciated ordinary chondrites. Fragments of primary rock in CM chondrites do not contain solar-wind-implanted gases [1] or preirradiated grains. This confirms the view that the dust mantles around various components of these rocks are the products of dust accretion in the solar nebula rather than of regolith processes on the parent body surface. References: [1] Metzler K. et al. (1992) GCA, 56, 2873. [2] Kerridge J. (1992) personal communication. [3] Krishnaswami S. et al. (1971) Science, 174, 287. [4] Goswami J. N. and Lal D.(1979) Icarus, 40, 510. [5] Goswami J. N. and MacDougall J. D. (1983) Proc. LPSC 13th, in JGR, 88, A755. [6] MacDougall J. D. and Phinney D. (1977) Proc. LSC 8th, 293.

  4. Petrogenesis and Nd-, Pb-, Sr-isotope geochemistry of the Cenozoic olivine melilitites and olivine nephelinites (ankaratrites) in Madagascar

    NASA Astrophysics Data System (ADS)

    Melluso, Leone; le Roex, Anton P.; Morra, Vincenzo

    2011-12-01

    The Cenozoic ankaratrites of the Alaotra, Takarindoha-Vatomandry and Votovorona (NE Ankaratra) volcanic fields, Madagascar, range from olivine ( monticellite) melilitites, through olivine-melilite nephelinites to olivine ( leucite) nephelinites. The rocks show significant compositional ranges in their coexisting magmatic minerals (olivine-group minerals, melilite, clinopyroxene, nepheline, leucite, Ba-phlogopite, perovskite, ilmenite, spinels, apatite), and evidence of distinct parental magmas, often in different facies of the same vent. Primitive compositions (high Mg#, Cr and Ni concentrations) are found in each volcanic district, and a few lavas contain mantle xenoliths or xenocrysts. The rocks show enrichment in the most strongly incompatible elements (e.g., Ba and Nb up to 200 times primitive mantle, La/Ybn = 24 to 40), with troughs at K and smooth, decreasing patterns towards the least incompatible elements in mantle-normalized diagrams. The Nd-Pb-Sr isotope geochemistry indicates a marked heterogeneity of the mantle sources of the various districts (e.g., 206Pb/204Pb = 18.68-18.77, 87Sr/86Sr = 0.704011-0.704207 for the Alaotra-Votovorona districts; 206Pb/204Pb = 19.04-19.14, 87Sr/86Sr = 0.703544-0.704017 for the Takarindoha-Vatomandry districts), with significant differences to other Cenozoic mafic volcanic rocks of northern Madagascar. The genesis of the Madagascan ankaratrites is related to rifting events which triggered low-degree partial melting of a garnet peridotite enriched in dolomite and incompatible-element-rich phases, in the lowermost lithosphere. Despite marked geochemical similarities, the source of the Madagascan melilitites bears no isotopic similarity to the HIMU-related sources of melilitites of eastern and southern Africa.

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

    To investigate the early history of olivine from the Main-Group pallasites Brahin and Brenham, we have spatially mapped their trace-element distributions using laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS). Brahin olivine interiors contain ˜100-200 μm patches enriched in Cr, Al, Ti, V, Sc and Ga, separated by linear enrichments of P; these structures bear no relation to current crystal morphologies. Rather, cross-cutting relationships suggest they predate olivine-metal mixing. Brenham olivine also has internal variations for these elements. By contrast, Ni and Co concentrations in olivine from both meteorites decrease near crystal margins, as expected for freezing-in of profiles formed during diffusive re-equilibration with metal during cooling. Brenham olivine also has decreasing Al, Cr and Ti near the margin. Correlations between concentrations of Cr and Al exist for individual Brahin olivine grains, but do not hold over multiple grains, indicating a heterogeneous precursor. Al and Ti are correlated over multiple grains in Brahin, interpreted as Ti cations decorating pre-existing Al-defects. In Brenham olivine, similar geochemical trends exist, but the Cr-Al relationship probably represents both grain margin effects and pre-existing internal heterogeneity. The preservation of structure for elements which are normally fast diffusers in olivine hinges on coupled substitutions involving Al, which along with P diffuses much more slowly than most other elements under some conditions. Al concentrations in olivine are low and variable (3-33 ppm) which is inconsistent with crystallisation from a normal silicate melt; Al-in-olivine thermometers indicate that pallasite olivine was formed in a low-temperature environment. Following its delivery to the magma ocean/core-mantle boundary, Al-P systematics were not substantially modified. Assuming diffusivities for Al and P that are similar to Si (since they reside in the same crystallographic site) and temperatures of 1600-1650 K (from the melting point of the metal and the absence of orthopyroxene in pallasites) an upper limit on the residence time of pallasite olivine of ˜1 Ma can be inferred by the persistence of trace element detail over scales of 100 μm. Following the olivine-metal mixing event, homogeneous Ni and Co distributions were modified by diffusion; Cr and V were partially modified; Al and P were essentially unchanged.

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

    NASA Astrophysics Data System (ADS)

    Blaha, Stephan; Katsura, Tomoo

    2013-04-01

    Knowledge of rheological properties of Earth's materials is essential to understand geological processes. Open questions are the water content and crystallographic orientation dependences of dislocation creep rate, because the dominant slip system changes with increasing water content, which suggest different dislocations have different water content dependence. This project focuses on olivine, which is the most abundant mineral of the upper mantle. It is also considered to be the weakest phase and hence should control the rheology of the upper mantle. Several slip systems were reported for olivine, which are [100](010), [001](010), [001](100) and [100](001), each of which appear under different water content and stress conditions [1]. For this purpose we started to obtain data for 'dry' conditions, providing basic knowledge to understand the effect of water. Variation in dislocation creep rate according to change in physical conditions can be estimated by dislocation recovery experiments [2]. In this technique, deformed crystals are annealed, in which the dislocation density is expected to decrease due to coalescence of two dislocations. Dislocation densities are measured before and after the annealing. Dislocation mobility, which should be directly proportional to the dislocation creep rate, is estimated based on the change in dislocation density and duration of annealing. This technique has significant advantages partly because informations of strain rate and deviatoric stress, which are difficult to measure, are unnecessary, and partly because dislocation annealing is conducted under quasi-hydrostatic conditions, which allows wide ranges of P and T conditions. The first step of the experiments is to deform a single crystal of olivine. For this purpose, we developed an assembly, which deforms a single crystal in simple-shear geometry and prevent breakage, sub-grain formation and recrystallization of the crystal. Olivine single-crystals were placed in the high-pressure assembly so that a particular slip system is activated. The assemblies were compressed to 3 GPa. The shear deformation was conducted at 1600 K. EBSD measurements indicate that the recovered crystals are single crystals and sub-grain formation did not occur in most cases. The second step is to anneal the samples under the same P-T conditions as those of the deformation experiments. Annealing experiments are also performed at ambient pressures at 1600 K. Dislocation density was measured by means of the oxidation decoration technique [3]. The samples were firstly polished and then oxidized at 1200 K for 50 min. The dislocations are preferably oxidized, so that presence of dislocation can be observed using SEM. First Results indicate that the dislocation density decreased by annealing by 1/4 with an annealing period of 10 h for dislocations with b = [001]. References [1] H. Jung and S. I. Karato. Water-induced fabric transitions in olivine. Science, 293(5534):1460-1463, 2001. [2] S. I. Karato, D. C. Rubie, and H. Yan. Dislocation recovery in olivine under deep upper mantle conditions: Implications for creep and diffusion. Journal of Geophysical Research, 98(B6):9761-9768, 1993. [3] D. L. Kohlstedt, C. Goetze, W. B. Durham, and J. V. Sande. New technique for decorating dislocations in olivine. Science, 191(4231):1045-1046, March 1976.

  7. The morphology and surface features of olivine in kimberlite lava: implications for ascent and emplacement mechanisms

    NASA Astrophysics Data System (ADS)

    Jones, T. J.; Russell, J. K.; Porritt, L. A.; Brown, R. J.

    2013-12-01

    Many kimberlite rocks contain large proportions of ellipsoidal-shaped xenocrystic olivine grains that are derived mainly from the disaggregation of peridotite. Xenocrystic olivine grains from a lava erupted from the Quaternary Igwisi Hills kimberlites, Tanzania, are compared to phenocrystic olivine, liberated from picritic lavas, and mantle olivine, liberated from a fresh peridotite xenolith, in order to examine the potential modification of olivine surface textures due to transport from the mantle to the surface within kimberlite magmas. Image analysis, SEM imagery and laser microscopy reveals significant differences in the surface features and morphologies of the three crystal populations. Xenocrystic olivine grains are characterised by rough surfaces, ellipsoidal shapes and impact pits. Mantle olivines are characterised by flaked surfaces and indented shapes consistent with growth as a crystal aggregates. Phenocrystic olivines are smooth-surfaced and exhibit flat crystal faces. We infer that the distinctive shapes and surfaces of xenocrystic olivine grains resulted from three distinct mechanical processes attending their rapid transport from their source in the mantle lithosphere: (1) penetrative flaking from micro-tensile failure induced by rapid decompression; (2) sustained abrasion and attrition arising from particle-particle collisions between grains in a turbulent, volatile-rich flow regime, and; (3) higher energy particle-particle collisions that produced impact cavities superimposed on decompression structures. The combination of these processes during the rapid ascent of kimberlite magmas is responsible for the distinctive ellipsoidal shape of olivine xenocrysts found in kimberlites worldwide.

  8. 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.

  9. 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.

  10. 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]. K? 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 ?m, pixel spacing of 1-2 ?m, 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 ?m 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 low P chambers and P enriched zones were also observed; near the margins of the crystals is possible to find the presence of discontinuous sets of P-enriched bands that generally outline euhedral crystal forms; some crystals are characterized by P-enriched ghosts of relict crystals in their interior that are associated with probable undercooling and/or with an initial pulse of rapid crystal growth [8, 10]. Phenocrysts and microphenocrysts are frequently unzoned in major and minor divalent cations (Fe, Mg, Mn, Ca, Ni), but all are zoned in P. Variations in Cr and Al correlate spatially with P but are much fainter or absents, in some crystal the P-enriched bands are superimposed with small crystals of chromite (?1 ?m) aligned along the P zoning. Probably these chromites were formed by precipitation from the original Cr and Al bands. In no case was observed Ti zoning. [1] Richter D.H. et al. (1970) US Geol Surv Prof Pap 537-E, 73 p. [2] Richter D.H., Moore J.G. (1966) US Geol Surv Prof Pap 537-B, 26 p. [3] Helz R.T. (1980) Bull Volcanol 43-4, 675-701. [4] Helz R.T. et al. (1984) US Geol Surv Open File Rep 84-484, 72 p. [5] Hardee H.C. et al. (1981) Geophys Res Lett 8, 1211-1214. [6] Helz R.T., Wright T.L. (1983) US Geol Surv Open File Rep 83-326, 66 p. [7] Helz R.T. (1987) Geochem Soc Spec Pub 1, 241-258. [8] Beckett J.R. et al. (2008) LPSC abs. 1726. [9] Mccanta M.C. et al. (2008) LPSC abs. 1807. [10] Milmann-Barris M.S. et al. (2008) CMP 155, 739-765. [11] Mccanta M.C. et al. (2008) GCA 72-12, S1, A610.

  11. 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 generally, this study questions the approach which consists in evaluating the carbonation potential of a rock based on experiments on separate minerals. It also emphasizes the impact of fO2 and potential co-injected gases on the olivine dissolution-carbonation process.

  12. Nepheline and sodalite in a barred olivine chondrule from the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Lumpkin, G. R.

    1980-01-01

    The discovery of nepheline and sodalite in association with glass in a barred olivine chondrule from the Allende C3V meteorite is reported, and the possible origin of the minerals is discussed. Scanning electron microscope/energy dispersive analysis indicates that the major minerals of the chondrule are olivine, bronzite and chromite, with olivine bars separated by glass of nearly pure plagioclase composition. The olivine is observed to have a composition richer in Fe than that predicted from olivine-liquid equilibria, indicating, along with the presence of plagioclase glass and small amounts of subcalcic diopside, the nonequilibrium crystallization of the barred olivine chondrule. The textural features of the chondrule are consistent with a liquid origin for nepheline and sodalite from the chondrule-forming liquid under nonequilibrium conditions.

  13. Olivine-Wadsleyite-Pyroxene Epitaxy: Element and Volatile Distributions at the 410km Discontinuity

    NASA Astrophysics Data System (ADS)

    Smyth, J. R.; Miyajima, N.; Huss, G. R.; Hellebrand, E.; Rubie, D. C.; Frost, D. J.

    2010-12-01

    We have synthesized hydrous peridotite-composition samples at 13GPa and 1400C with co-existing coarse grains (~100 micrometer) of olivine, wadsleyite, clinoenstatite, and melt in a multi-anvil press. The olivine grains contain fine-scale lamellae of wadsleyite and clinoenstatite that likely resulted from small temperature fluctuations during the four-hour experiment. Major-element compositions were determined by electron microprobe and H contents by secondary ion mass spectroscopy (SIMS). The olivine is about Fo93 in composition and contains about 650 ppm by weight H2O. The wadsleyite is about Fo87 in composition and contains about 1650 weight percent H2O. The clinoenstatite is about En96 in composition and about 440 ppm H2O. High resolution transmission electron microscopy of the lamellae and host show that the olivine and wadsleyite share their close-packed oxygen planes so that the wadsleyite lamellae are nearly planar and perpendicular to the [1 0 0] of olivine. The wadsleyite lamellae thus have their [1 0 1] and [1 0 -1] directions parallel to the [1 0 0] of olivine. Additionally, a second orientation relation with the [001] of olivine parallel to [100] of wadsleyite is also found as are incoherent blebs of wadsleyite in olivine. The coexisting melt phase quenched to a feathery mass of mostly wadsleyite crystals. Neither a quenched glass phase nor a nominally hydrous phase was observed. The lamellae indicate that the olivine-wadsleyite transformation can proceed effectively by coherent mechanisms that could potentially preserve lattice preferred orientation. The observed rapid coherent inversion from olivine to wadsleyite means that a metastable preservation of olivine below 410 km is unlikely under slightly hydrous conditions. The distribution of H among the nominally anhydrous phases implies that dehydration of peridotites by partial melting is inefficient so that complete dehydration of subducting slabs is unlikely. SEM-BSE image of wadsleyite (W) blebs and lamellae in olivine (O).

  14. 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.

  15. [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

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

    USGS Publications Warehouse

    Page, N.J.

    1976-01-01

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

  17. 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.

  18. 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.

  19. 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.

  20. 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 low activation energy, somewhat similar to that of unshocked alkali feldspar, despite remaining a high temperature mineral due to a much lower frequency factor. References: [1]Jessberger E. K. and Ostertag R. (1982). GCA 46:1465-1471. [2]Stephan T. and Jessberger E. K. (1992). GCA 56:1591-1605.

  1. 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 basaltic melt composition), consistent with fO2 values obtained by assuming olivine-silica-iron metal (OSI) equilibrium. For the primary chromite-bearing-ureilites, the corresponding fO2 were estimated (again, assuming basaltic melt composition) to be ∼IW to IW+1.0, i.e., several orders of magnitude more oxidizing than the conditions estimated for the chromite-free ureilites. In terms of Fo and Cr valence properties, ureilites appear to form two groups rather than a single “Cr-valence (or fO2) vs. Fo” trend. The chromite-bearing ureilites show little variation in Fo (∼74-76) but significant variation in Cr valence, while the non-chromite-bearing ureilites show significant variation in Fo (∼77-95) and little variation in Cr valence. These groups are unrelated to petrologic type (i.e., olivine-pigeonite, olivine-orthopyroxene, or augite-bearing). The chromite-bearing ureilites also have lower contents of Cr in olivine than most non-chromite-bearing ureilites, consistent with predictions based on Cr olivine/melt partitioning in spinel saturated vs. non-spinel-saturated systems. Under the assumption that at magmatic temperatures graphite-gas equilibria controlled fO2 at all depths on the ureilite parent body, we conclude: (1) that ureilite precursor materials having the Fo and Cr valence properties now observed in ureilites are unlikely to have been preserved during planetary processing; and (2) that the Fo and Cr valence properties now observed in ureilites are consistent with having been established by high-temperature carbon redox control over a range of depths on a plausible-sized ureilite parent body. The apparent limit on ureilite Fo values around 74-76 suggests that the precursor material(s) had bulk mg# ⩾ that of LL chondrites.

  2. Experimental constraints of the olivine crystals compaction in cumulus layer

    NASA Astrophysics Data System (ADS)

    Forien, M.; Bagdassarov, N.; Schmidt, M. W.

    2009-12-01

    The layered intrusions are the result of magma crystallization and differentiation in a form of lateral structures, which are often observed in magmatic chambers. They are markers of processes occurring during a prolonged cooling stage (several tens of thousands years for bodies 1 km in size). There is no unique explication for the mechanism of layering during the intrusion formation. The most plausible mechanism proposed to explain the observed layering includes the coupled crystal settling and residual liquid advection. In the layers containing a large crystal fraction (> 66 vol%) and a small percentage of the residual liquid, the compaction mechanism and the decrease of cumulate layer porosity due to the diffusion adjustment of grain boundaries could effectively occur. In this study, the compaction mechanisms of crystals settling in magma chambers have been modelled with the use of a high temperature centrifuge. The suspensions of olivine crystals and a basaltic melt (33 vol% and 67 vol%, respectively) were centrifuged at the melting temperature of basalt (temperature range of 1270-1280°C). The experiments were conducted at 200-1500 g under a pressure between 0.8-1.1 GPa. During centrifugation run olivine grains are compacted because of the x-time enhanced centrifugation force which is equivalent to x-time larger volume of crystals compacting from above. After crystals have reached a maximum compaction concentration due to this accelerated piling from above, their locations and porosity in cumulates change under the influence of the solution - recrystallisation process. The concentration of crystals in a cumulate layer increases much slower than during their sedimentation. The solution-precipitation and recrystallisation process is a diffusion type mechanism of compaction and has not been addressed experimentally before. Evidences of the precipitation - recrystallisation process of olivine grains in centrifuged samples with TEM analyses are revealed. In fact, knowing that Ca is characteristic only for MORB-melt, the first feature is the presence of Ca at the interface of two adjacent Ol-grains even when the melt phase is escaped. Another evidence of the diffusion compaction is the presence of some small melt inclusions at the growing Ol-boundaries of compacting Ol-grains. Finally, the precipitation - recrystallisation process of olivine grains during the cumulus compaction stems from the observation that the new boundary between two Ol-grains is distinct and not fully crystallized as the interior of grains. This indicates some MORB melt elements (for example, enrichment in Ca) prevent to recrystallize Ol in a fully crystalline structure.

  3. 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.

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

    USGS Publications Warehouse

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

    1987-01-01

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

  5. 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 systems.

  6. 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.

  7. Annealing behaviour of ion tracks in olivine, apatite and britholite

    NASA Astrophysics Data System (ADS)

    Afra, B.; Lang, M.; Bierschenk, T.; Rodriguez, M. D.; Weber, W. J.; Trautmann, C.; Ewing, R. C.; Kirby, N.; Kluth, P.

    2014-05-01

    Ion tracks were created in olivine from San Carlos, Arizona (95% Mg2SiO4), apatite (Ca5(PO4)3(F,Cl,O)) from Durango, Mexico, and synthetic silicates with the apatite structure: Nd8Sr2(SiO4)6O2 and Nd8Ca2(SiO4)6O2 using 1.6 and 2.2 GeV Au ions. The morphology and annealing behaviour of the tracks were investigated by means of synchrotron based small angle X-ray scattering in combination with ex situ annealing. Tracks in olivine annealed above ∼400 °C undergo a significant change in track radius due to recrystallisation of the damage tracks. At temperatures higher than 620 °C, the scattering images indicate fragmentation of the track cylinders into smaller subsections. Ion tracks were annealed at elevated temperatures up to 400 °C in the Durango and Ca-britholite, and up to 560 °C in Sr-britholite. While there was a significant change in the track radii in the Durango apatite, tracks in the two synthetic samples remained almost unchanged.

  8. 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.

  9. 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.

  10. 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.

  11. The interaction between deformation and hydration: Physico-chemical alteration and replacement of naturally deformed olivine

    NASA Astrophysics Data System (ADS)

    Plümper, Oliver; Piazolo, Sandra; Austrheim, Hâkon

    2010-05-01

    Deformation and fluid-mediated reactions are essentially interrelated and thus it is crucial to understand the mechanisms that govern the interaction between them. Natural olivine grains frequently display microstructural evidence of plastic deformation, such as the alignment of planar arrays of dislocations forming subgrain boundaries. We have examined deformed olivine from ophiolitic metaperidotites in Norway to investigate the influence of intragranular microtextures created by deformation on fluid-mediated replacement reactions. Optical and scanning electron microscopy show a striped chemical zoning parallel to the typical olivine kink banding and the optical undulose extinction. Fe-enriched and Fe-depleted zoning are found that have distinct, parallel spacing across the olivine grains. The most pronounced striped zoning is found to spread out from serpentine needles that cut into the olivine. Focused ion beam sample preparation technique and transmission electron microscopy reveal that the striped chemical zoning is associated with (100)ol subgrain boundaries composed of edge dislocations that are formed during plastic deformation. Nanometer-sized serpentine clusters are found at subgrain boundaries associated with the Fe-depleted zoning. The replacement of olivine by serpentine originating at these subgrain boundaries indicates that they can act as pathways for fluid infiltration. However, subgrain boundaries associated with Fe-enriched zoning show no evidence for olivine replacement by serpentine. From the striped zoning and serpentine replacement we infer that (100)ol subgrain boundaries, the locus of edge dislocation piling, potentially channels fluid entry, as has also been recently suggested by Boudier et al. (in press). In conjunction with the zoning, the investigated olivine grains have a tendency to develop preferentially orientated parting, mimicking a well developed cleavage. Electron backscatter diffraction (EBSD) reveals a complex orientation relationship between the parting formation and the replacement process. Olivine grains have the textural appearance of a single grain but are divided into highly misorientated domains. However, the parting propagates throughout the seemingly single olivine grain despite the large misorientation of the domains. Grains showing parting are surrounded by olivine that is replaced by serpentine with the typical mesh texture. Backscattered electron imaging from scanning electron microscopy showed that the formation of the preferred orientated parting is closely related to the replacement of olivine by elongated diopside grains orientated parallel to the parting. Our observations indicate that the plastic deformation of olivine has the potential to channel the entry of fluids. This would have an important influence on the homogeneity of fluid infiltration and hence the hydration of olivine to form serpentine. Therefore, fluid infiltration and the resulting mineral replacement reactions are strongly dependent on the plastic deformation of olivine prior to replacement. References: Boudier et al. (in press), J. Petrol.

  12. Morphology and surface features of olivine in kimberlite: implications for ascent processes

    NASA Astrophysics Data System (ADS)

    Jones, T. J.; Russell, J. K.; Porritt, L. A.; Brown, R. J.

    2014-05-01

    Most kimberlite rocks contain large proportions of ellipsoidal-shaped xenocrystic olivine grains that are derived mainly from disaggregation of peridotite. Here, we describe the shapes, sizes and surfaces of olivine grains recovered from kimberlite lavas erupted from the Quaternary Igwisi Hills volcano, Tanzania. The Igwisi Hills kimberlitic olivine grains are compared to phenocrystic olivine, liberated from picritic lavas, and mantle olivine, liberated from a fresh peridotite xenolith. Image analysis, scanning electron microscopy imagery and laser microscopy reveal significant differences in the morphologies and surface features of the three crystal populations. The kimberlitic olivine grains form smooth, rounded to ellipsoidal shapes and have rough flaky micro-surfaces that are populated by impact pits. Mantle olivine grains are characterised by flaked surfaces and indented shapes consistent with growth as a crystal aggregate. Phenocrystic olivine exhibit faceted, smooth-surfaced crystal faces. We suggest that the unique shape and surface properties of the Igwisi Hills kimberlitic olivine grains are products of the transport processes attending kimberlite ascent from mantle source to surface. We infer that the unique shapes and surfaces of kimberlitic olivine grains result from three distinct mechanical processes attending their rapid transport through the thick cratonic mantle lithosphere: (1) penetrative flaking from micro-tensile failure induced by rapid decompression; (2) sustained abrasion and attrition driven by particle-particle collisions between grains within a turbulent, volatile-rich flow regime; and (3) higher-energy particle-particle collisions producing impact cavities superimposed on decompression structures. The combination of these processes during the rapid ascent of kimberlite magmas is responsible for the distinctive ellipsoidal shape of olivine xenocrysts found in kimberlites worldwide.

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

    NASA Astrophysics Data System (ADS)

    Sobolev, Alexander; Batanova, Valentina

    2015-04-01

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

  14. 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

  15. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

    Secondary Ion Mass Spectrometry (SIMS) data for Ni, Co, Cr, and V in olivine in martian basalts is compared to data from lunar and terrestrial basalts. We use experimentally-derived and published D values to calculate as-yet unsampled, olivine-bearing, non-cumulus melt compositions. Additional information is contained in the original extended abstract.

  17. Flow Mechanisms of San Carlos olivine at high pressure

    NASA Astrophysics Data System (ADS)

    Li, L.; Weidner, D.; Chen, J.; Raterron, P.; Vaughan, M.

    2002-05-01

    Flow mechanisms for San Carlos olivine at pressures up to 8 GPa and temperatures up to 1500K are investigated using synchrotron x-radiographic techniques. TEM observations on recovered samples are used to define the microstructures and illuminate processes. We conclude that dislocation creep assisted by dynamic recrystallization dominates deformation of polycrystalline San Carlos olivine above 1000K with little dependence on grain boundary sliding and no indication of a grain-size dependence of flow. Below this temperature dislocation glide, also assisted by dynamic recrystallization, dominates deformation. Strain rates derived from the digital images of stressed samples have the precision up to 10-6s-1. Two piggy-backed San Carlos olivine specimens have average grain sizes of 0.5 μ m and 5 μ m. Each specimen achieves a total of 6-7% strain after heating process begin. With identical differential stress states, and for a range of temperatures, the strain rates for both specimens are virtually identical indicating the absence of a grain-size sensitive flow process in these experiments. This implies that an activation volume of 5 cc/mole or less for `power-law-creep' is required to define the boundary between grain-size sensitive flow (diffusion creep) and grain-size insensitive flow (dislocation creep). TEM observations reveal that grain sizes of both samples remained different by at least a factor of 2 during the entire experiment. However, indications of dynamic recrystallization and grain-growth are observed in the samples. Often, the grain size of the fine-grain sample increased while that of the coarse-grain sample decreased during the same experiment indicating that the grain size of both samples are controlled by dynamic recrystallization. No evidence of grain boundary sliding is found in our samples. Strain contrasts are widespread at grain boundaries before dynamic recrystallization is fully activated. Well-equilibrated samples are accompanied by triple-junctions rather than the quad-junctions which are typical of active grain boundary sliding. Taken together with the grain-size insensitivity of the flow process, we conclude that there are no`super-plastic' mechanisms active in these experiments.

  18. Dynamic Recrystallization of Olivine Aggregates During High-strain Deformation

    NASA Astrophysics Data System (ADS)

    Bystricky, M.; Kunze, K.; Burlini, L.

    2001-12-01

    We have investigated the high shear strain behaviour of polycrystalline olivine aggregates using a high-pressure, high-temperature Paterson torsion apparatus. Olivine samples hot-pressed from San Carlos powders were deformed at temperatures of 1200-1250° C, a confining pressure of 300 MPa, and an oxygen fugacity near either the Fe/FeO or the Ni/NiO buffer. The experiments were performed in the dislocation creep field, at constant twist rates corresponding to shear strain rates of 3*E-5}s{-1 to 3*E-4}s{-1, to total shear strains of up to 7. Experiments on natural dunites from Kohistan, Pakistan, are now being performed under similar conditions. In all the experiments on hot-pressed aggregates, deformation appeared to be steady-state up to shear strains of γ ~0.2. The peak stress values were consistent with previous rheological data on the dislocation creep of olivine obtained in compression experiments under dry conditions. After the initial peak stress, progressive weakening occurred with strain, leading to a total weakening of the aggregate of ~15-25% at γ >4. At high shear strains (γ =5 to 7), softening was less and less pronounced, suggesting nearly steady-state behaviour. Stepping tests performed at various shear strains yielded stress exponents of ~3.2, typical of deformation by dislocation creep. FTIR analyses of deformed samples indicate that deformation occurred under essentially dry conditions (<30 ppm H/Si). Simple shear microstructures and lattice preferred orientations were analyzed using optical microscopy and electron backscatter diffraction. At strains up to γ ~0.5, microstructural analyses show evidence for dislocation creep and recovery in the form of deformation lamellae. Highly irregular grain boundaries with multiple bulges suggest incipient recrystallization by grain boundary migration. Subgrain rotation recrystallization appears to dominate at higher strains, as evidenced by multiple subgrains and core-and-mantle structures. At strains of γ >=5, recrystallization is nearly complete, with the formation of a strong foliation sub-parallel to the shear plane. About ~5% of remaining porphyroclasts consist of ribbons with highly stretched tails and asymmetric porphyroclasts showing subgrains and deformation features. There is no microstructural evidence for any shear localization. During the deformation, the texture evolved through a transient deformation texture (γ ~0.5) with [100] axes distributed oblique to the shear direction, into a recrystallization texture (γ ~5) with sharp [100] maxima parallel to the shear direction and girdles of [010] and [001] normal to that direction, consistent with "easy slip" on the (010)[100] system.

  19. 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.

  20. Extended planar defects and the rapid incorporation of Ti4+ into olivine

    NASA Astrophysics Data System (ADS)

    Burgess, Katherine D.; Cooper, Reid F.

    2013-10-01

    The formation of extended planar defects in minerals such as olivine is related to high point defect concentration and can be driven by large gradients in chemical potential, where the energy of the system is lowered by the ordering of defects along specific planes in the crystal. The presence of extended defects has the potential to create the (apparently) anomalous ionic diffusion in olivine as reported recently (Spandler and O'Neill in Contrib Mineral Petrol 159(6):791-818, 2010). High-resolution transmission electron microscopy and energy-filtered imaging were done using experimental samples designed to examine the impact of a TiO2 and f O2 on the potential to form such defects in ferromagnesian olivine. Doped basalt (5 wt% TiO2)-olivine reaction couple experiments were run at 1 atm and 1,310 and 1,410 °C for 50 h at various f O2, ranging from 102 below to 102 above the quartz-fayalite-magnetite buffer. Our results show that extended planar defects in olivine, parallel to {101}ol and occurring in ordered "clusters" with a prolate spheroid geometry 5-25 nm across and extending up to 150 nm into the olivine, are present near the olivine-glass interfaces in all of our experimental high-TiO2 basalt-olivine samples. Increased Ti content in the olivine is associated with the defects; ordering of Ti4+ and octahedral site vacancies leads to a two- or three-layer superstructure in the olivine. Defect nucleation and growth is driven by the large TiO2 chemical potential gradient across the phase boundary at the start of the experiments, which provides access to microstructures not otherwise present.

  1. Remote compositional analysis of lunar olivine-rich lithologies with Moon Mineralogy Mapper (M3) spectra

    USGS Publications Warehouse

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

    2011-01-01

    A systematic approach for deconvolving remotely sensed lunar olivine-rich visible to near-infrared (VNIR) reflectance spectra with the Modified Gaussian Model (MGM) is evaluated with Chandrayaan-1 Moon Mineralogy Mapper (M 3) spectra. Whereas earlier studies of laboratory reflectance spectra focused only on complications due to chromite inclusions in lunar olivines, we develop a systematic approach for addressing (through continuum removal) the prominent continuum slopes common to remotely sensed reflectance spectra of planetary surfaces. We have validated our continuum removal on a suite of laboratory reflectance spectra. Suites of olivine-dominated reflectance spectra from a small crater near Mare Moscoviense, the Copernicus central peak, Aristarchus, and the crater Marius in the Marius Hills were analyzed. Spectral diversity was detected in visual evaluation of the spectra and was quantified using the MGM. The MGM-derived band positions are used to estimate the olivine's composition in a relative sense. Spectra of olivines from Moscoviense exhibit diversity in their absorption features, and this diversity suggests some variation in olivine Fe/Mg content. Olivines from Copernicus are observed to be spectrally homogeneous and thus are predicted to be more compositionally homogeneous than those at Moscoviense but are of broadly similar composition to the Moscoviense olivines. Olivines from Aristarchus and Marius exhibit clear spectral differences from those at Moscoviense and Copernicus but also exhibit features that suggest contributions from other phases. If the various precautions discussed here are weighed carefully, the methods presented here can be used to make general predictions of absolute olivine composition (Fe/Mg content). Copyright ?? 2011 by the American Geophysical Union.

  2. 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.

  3. Mantle-crust interactions in the oceanic lithosphere: Constraints from minor and trace elements in olivine

    NASA Astrophysics Data System (ADS)

    Sanfilippo, Alessio; Tribuzio, Riccardo; Tiepolo, Massimo

    2014-09-01

    Minor and trace element compositions of olivines are used as probes into the melt-rock reaction processes occurring at the mantle-crust transition in the oceanic lithosphere. We studied mantle and lower crustal sections from the Alpine Jurassic ophiolites, where lithospheric remnants of a fossil slow-spreading ocean are exposed. Olivines from plagioclase-harzburgites and replacive dunites (Fo = 91-89 mol%) and from olivine-rich troctolites and troctolites (Fo = 88-84 mol%) were considered. Positive correlations among the concentrations of Mn, Ni, Co, Sc and V characterize the olivines from the dunites. These chemical variations are reconciled with formation by melts produced by a mixed source consisting of a depleted peridotite and a pyroxene-rich, garnet-bearing component melted under different pressure conditions. We thereby infer that the melts extracted through these dunites channels were not fully aggregated after their formation into the asthenospheric mantle. Olivines from the olivine-rich troctolites and the troctolites are distinct by those in the dunites by lower Ni and higher concentrations of Mn and incompatible trace elements (Ti, Zr, Y and HREE). Fractional crystallization cannot reproduce the chemical variations of the olivines from the olivine-rich troctolites and the troctolites. In these rock-types, the olivines commonly show heterogeneous Ti, Zr, Y and HREE compositions, which produce variable Ti/Y and Zr/Y values. We correlate these olivine characteristics with events of reactive melt migration occurred during the formation of the primitive lower oceanic crust. We propose that the migrating melts formed at the mantle-crust transition via interaction with mantle peridotites during periods of low melt supply.

  4. Additional Sr Isotopic Heterogeneity in Zagami Olivine-Rich Lithology

    NASA Technical Reports Server (NTRS)

    Misawa, K.; Niihara, T.; Shih, C.-Y; Reese, Y. D.; Nyquist, L. E.; Yoneda, S.; Yamashita, H.

    2012-01-01

    Prior isotopic analyses of Zagami have established differing initial Sr-87/Sr-86 (ISr) ratios of among Zagami lithologies, fine-grained (FG), coarse-grained (CG), and dark mottled lithologies (DML)]. The Zagami sample (KPM-NLH000057) newly allocated from the Kanagawa Prefectural Museum of Natural History contained DML and the Ol-rich lithology which included more ferroan olivines (Ol-rich: Fa(sub 97- 99) vs late-stage melt pockets: Fa(sub 90-97)]). We have combined mineralogy-petrology and Rb-Sr isotopic studies on the Kanagawa Zagami sample, which will provide additional clues to the genesis of enriched shergottites and to the evolution of Martian crust and mantle

  5. 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.

  6. Phyllosilicate and Olivine around a Fracture in Nili Fossae

    NASA Technical Reports Server (NTRS)

    2007-01-01

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) took this observation of part of the Nili Fossae region at the western margin of the Isidis impact basin at 3:07 (UTC) on December 12, 2006, near 21.9 degrees north latitude, 78.2 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 a gigantic impact on the surface of Mars early in the planet's history. The image of the Isidis basin at the top left is the colored elevation data from the Mars Orbiter Laser Altimeter (MOLA) overlain on a digital image mosaic from the Viking mission. Reds represent higher elevations, and blue lower elevations. The western rim of the Isidis basin has numerous, concentric troughs (or 'fossae') which may have formed during faulting associated with the impact event. Since then, the Nili Fossae region has since been heavily eroded, and is one of the most mineralogically diverse spots on Mars.

    This CRISM image targets one of region's smaller fractures. The image is shown overlain on the Viking digital image mosaic at lower left. The lower right CRISM image was constructed from three visible wavelengths (0.71, 0.60 and 0.53 microns in the red, green and blue image planes, respectively) and is close to what the human eye would see. The blue on the right of the image is an artifact from light scattering in the atmosphere. The upper right image was constructed from three infrared channels (2.38, 1.80 and 1.15 microns in the red, green and blue image planes, respectively) to highlight the mineralogy of the area. The bright green areas are rich in 'phyllosilicates,' a category of minerals including clays. The purple material along the walls of the fracture likely contains small amounts of the iron- and magnesium-rich mineral pyroxene. The yellow-brown material contains the 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.

  7. Serpentinization of Sintered Olivine during Seawater Percolation Experiments

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    Hydration of the mantle lithosphere exposed at slow spreading ridges leads to significant changes of the rock rheological, geophysical, mineralogical and geochemical properties, and to the production of large amounts of H2 and CH4, and of complex carbon molecules that support primitive ecosystems. The onset and efficiency of these hydrothermal processes requires penetration and renewal of fluids at the mineral-fluid interface. However, the mechanisms and the depth of fluid penetration are still poorly understood. Moreover, serpentinization is exovolumic, if a mass-conservative system is assumed, or chemical elements are leached out to conserve rock volume. Thus, the durability and extent of serpentinisation depends of the system capacity to create space and/or to drive mass transfers. In order to investigate these hydrodynamic and chemical mechanisms, we did a series of laboratory experiments during which seawater was injected in sintered San Carlos olivine samples at conditions representative of low temperature ultramafic hydrothermal systems. The percolation-reaction experiments were carried out using the ICARE 2 experimental bench at a confined pressure of 19 MPa and a temperature of 190°C; water flow was set at a constant specific discharge of 0.06 mL/h. During experiments (up to 23 days), permeability decreases continuously although the high Si concentrations in outlet fluids indicate steady olivine dissolution. Fluids are also depleted in Fe and Mg, suggesting precipitation of Fe- and Mg-rich mineral phases; SEM and AEM/TEM analyses of the reacted samples allowed to characterize hematite and poorly crystallized serpentine, both formed at the expense of olivine. Mass balance calculations indicate that, on average, 15 wt. % olivine was dissolved while the same mass of serpentine (+/- brucite) was formed; concurrently, porosity decreased from ~ 12% to 5 %. We infer that the structure of the newly formed serpentine resulted in the clogging of fluid paths and explain the decrease of permeability during experiments. Hematite (<1 wt.%) is also observed, indicating redox reactions. The estimated total hydrogen content of outlet fluids is 4.5 mmol/kg. Although these values are in the same range as those measured at the Lost City hydrothermal vent (e.g., Kelley et al, 2001), they are significantly lower than theoretical estimates of hydrogen composition of serpentinisation fluids (e.g., 21-170 mmol/kg, Wetzel & Shock, 2000). We infer that these differences result, in part, from poor fluid renewal at the mineral interface during experiments, and maybe also in natural systems. These experimental results are used to constrain numerical reactive transport models and better understand the scale and efficiency of serpentinization reactions (effective reaction rates in porous/fractured media) at the scale of spreading ridges. Ref.: Kelley et al., Nature, 412, 145-149, 2001; Wetzel & Shock, JGR, 105, 8319-8340, 2000.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Fe 2+-Mg partitioning between olivine and basaltic melts: Applications to genesis of olivine-phyric shergottites and conditions of melting in the Martian interior

    NASA Astrophysics Data System (ADS)

    Filiberto, Justin; Dasgupta, Rajdeep

    2011-04-01

    Fe 2+-Mg partitioning between olivine and basaltic melt, expressed by the exchange coefficient, K Dol - melt Fe - Mg [=( XmeltMg/ XolivineMg)/( XmeltFe 2 + / XolivineFe 2 + )] is widely used to check if a rock composition may represent a mantle-derived magma, to demonstrate equilibrium between coexisting olivine and groundmass in mafic-ultramafic systems, both in experiments and in natural assemblages, and to constrain liquid lines of descent where olivine is the dominant fractionating phase. However, K Dol - melt Fe - Mg of 0.30, which is appropriate for understanding most terrestrial basalts petrogenesis may not apply for Martian basalts as K Dol - melt Fe - Mg is known to depend strongly on the melt compositions and Martian systems produce basalts that are distinctly richer in iron than terrestrial basalts. Here we compiled experimental data on olivine-melt equilibria of Martian and terrestrial basalt compositions to parameterize the effect of magma composition on K Dol - melt Fe - Mg and derive the K Dol - melt Fe - Mg applicable for Martian magmatic systems. We find that the equilibrium relationship between olivine and basaltic melt in Martian systems is described by K Dol - melt Fe - Mg of 0.35 0.01. Applying the newly parameterized values of K Dol - melt Fe - Mg to olivine-phyric shergottites suggest that the only known Martian meteorites where the olivine cores and the bulk composition are in equilibrium and therefore could represent magma compositions are: Yamato 980459, NWA 5789, and NWA 2990. LAR 06319, which has been suggested to represent a near magma composition, actually contains ~ 11 wt.% excess olivine. All other ol-phyric shergottites contain significant excess olivine (20-52 wt.%). Further, assuming that the basalts analyzed by the Mars Exploration Rovers at Gusev crater and the Bounce Rock in Meridiani Planum lie on olivine control lines, we have used our newly parameterized K Dol - melt Fe - Mg to estimate primary magmas in equilibrium with the model Martian mantle. Application of geothermobarometers to new primitive magma compositions suggest that basalt generation in the Martian mantle occurs at greater depths and higher temperatures than previously thought.

  13. 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 rate at high temperature. Within these ribbons the olivine was coarsened and the iron metal globules coalesced to micron-sized grains. The ribbons also are mosaicized and cut by planar fractures, which bespeak a second shock event, possibly that of ejection from Mars. The deeply colored olivine in NWA 2737 is unusual and represents a new 'ground truth' type for remote sensing of Mars. Understanding the occurrence of the brown color in olivine in NWA 2737 places important constraints on interpretation of optical measurements.

  14. 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.

  15. 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.

  16. Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

    NASA Technical Reports Server (NTRS)

    Usui, T.; Shearer, C. K.; Righter, K.; Jones, J. H.

    2011-01-01

    Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

  17. 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.

  18. H Diffusion in Olivine and Pyroxene from Peridotite Xenoliths and a Hawaiian Magma Speedometer

    NASA Technical Reports Server (NTRS)

    Peslier, A. H.; Bizimis, M.

    2014-01-01

    Hydrogen is present as a trace element in olivine and pyroxene and its content distribution in the mantle results from melting and metasomatic processes. Here we examine how these H contents can be disturbed during decompression. Hydrogen was analyzed by FTIR in olivine and pyroxene of spinel peridotite xenoliths from Salt Lake Crater (SLC) nephelinites which are part of the rejuvenated volcanism at Oahu (Hawaii) [1,2]. H mobility in pyroxene resulting from spinel exsolution during mantle upwelling Most pyroxenes in SLC peridotites exhibit exsolutions, characterized by spinel inclusions. Pyroxene edges where no exsolution are present have less H then their core near the spinel. Given that H does not enter spinel [3], subsolidus requilibration may have concentrated H in the pyroxene adjacent to the spinel exsolution during mantle upwelling. H diffusion in olivine during xenolith transport by its host magma and host magma ascent rates Olivines have lower water contents at the edge and near fractures compared to at their core, while the concentrations of all other chemical elements appear homogeneous. This suggests that some of the initial water has diffused out of the olivine. Water loss from the olivine is thought to occur during host-magma ascent and xenolith transport to the surface [4-6]. Diffusion modeling matches best the data when the initial water content used is that measured at the core of the olivines, implying that mantle water contents are preserved at the core of the olivines. The 3225 cm(sup -1) OH band at times varies independantly of other OH bands, suggesting uneven H distribution in olivine defects likely acquired during mantle metasomatism just prior to eruption and unequilibrated. Diffusion times (1-48 hrs) combined with depths of peridotite equilibration or of magma start of degassing allow to calculate ascent rates for the host nephelinite of 0.1 to 27 m/s.

  19. Magnetic properties of natural and synthetic olivines: high-field measurements

    NASA Astrophysics Data System (ADS)

    Ferre, E. C.; Martin-Hernandez, F.

    2004-12-01

    Olivine [(Fex, Mg1-x)2 SiO4] is an orthosilicate solid solution between fayalite [Fe2 SiO4] and forsterite [Mg2 SiO4]. Olivine is a major constituent of the Earth mantle that is abundant in oceanic and continental peridotites and mantle xenoliths. The magnetic properties of olivines have been previously investigated using gem quality natural crystals known as peridots (Zabargad) or using laboratory grown synthetic crystals. Magnetic investigations are generally performed using low magnetic field or neutron diffraction techniques. Optical microscopy and TEM imagery reveal that most olivine crystals host iron oxides formed by exsolution during cooling. Theoretically, the magnetic susceptibility of olivine should decrease linearly from fayalite to fayalite as a function of the Fe content. The magnetic behavior should range from antiferromagnetic at high Fe content, paramagnetic at intermediate Fe contents and diamagnetic at very low Fe contents. New magnetic measurements, performed on various high field instruments (vibrating sample magnetometer, torque magnetometer, cantilever magnetometer), both on natural and synthetic samples, display ferromagnetic behavior, interpreted as due to the systematic presence of titanomagnetite inclusions in olivine crystals. These results emphasize the need to conduct measurements in high field in order to isolate the intrinsic paramagnetic properties of olivines. These measurements demonstrate the orthorhombic nature of the intrinsic paramagnetic properties, but also yield new data concerning the relationship between crystallographic axes, magnetic anisotropy and other physical anisotropies: [100] = K1, [010] = K2 and [001] = K3. Preliminary results also indicate substantial variations in degree of paramagnetic anisotropy (P) and paramagnetic shape factor (T). For Fo92, P = 1.359 and T = -0.845. These intrinsic paramagnetic properties are used to model the magnetic behavior of olivine across a range of temperatures relevant to planetary exploration. They are also used to evaluate the possible effects of olivine deformation on its intrinsic properties. For example, deformation-induced striped iron zoning is anticipated to strongly modify crystal magnetic anisotropy.

  20. Compositional Dependency of Space Weathering: Pulse Laser Irradiation and Reflectance Measurement on Olivine-Pyroxene Mixtures

    NASA Astrophysics Data System (ADS)

    Sasaki, S.; Kurahashi, E.

    2001-11-01

    Space weathering is proposed to explain spectral mismatch between asteroids and meteorites, especially between S-type asteroids and ordinary chondrites, as well as spectral difference between lunar soils and rocks. Recently it is established that the space weathering is caused by formation of nanophase iron particles around the surface regolith grains; iron nanoparticles are formed through deposition of silicate vapor from micrometeorite impact heating and/or solar wind sputtering [1, 2, 3, 4]. Using nanosecond pulse laser simulating micrometeorite impacts, we reproduced darkening and reddening of reflectance spectra of various silicate minerals [5]. From TEM analysis, we found that iron nanoparticles are ubiquitous in the amorphous rim around laser-irradiated olivine grains [3]. The change of reflectance is much more significant in olivine than in pyroxene even under similar iron contents; olivine-rich asteroids would be more easily weathered than pyroxene-rich asteroids [6]. Since the vapor-deposited rim around regolith grains is responsible for the reflectance change, there is a possibility that the space weathering degree does not directly reflect mineral composition in the surface regolith. For example, if surface regolith contains some amounts of olivine, the amorphous rim with iron nanoparticles would be also formed around pyroxene grains. Here, we simulated space weathering on samples of various mixing ratio between olivine and enstatite and between olivine and hypersthene. We examine overall spectra as well as continuum slope of infrared reflectance and 1 micron - 2 micron band area ratio. In our results, small amounts of olivine should enhance the reflectance change at olivine-enstatite mixture, whereas hypersthene mainly controls the reflectance spectra at olivine-hypersthene mixture. [1] Pieters, C. M. et al., MAPS 35, 1101, 2000. [2] Hapke, B. JGR 106, 10039, 2001. [3] Sasaki, S. et al., Nature 410, 555, 2001. [4] Clark, B. et al., in Asteroid III, 2002. [5] Yamada, M. et al., Earth Planets Space 51, 1255, 1999. [6] Hiroi, T. and Sasaki, S., MAPS in press, 2002.

  1. 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

  2. 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.

  3. 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.

  4. 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 occur in subduction zones where serpentinite is dragged down by plate movement. Topotactic growth of olivine may be an important cause of mantle anisotropy in convergent margins.

  5. Cellular Precipitates Of Iron Oxide in Olivine in a Stratospheric Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1996-01-01

    The petrology of a massive olivine-sulphide interplanetary dust particle shows melting of Fe,Ni-sulphide plus complete loss of sulphur and subsequent quenching to a mixture of iron-oxides and Fe,Ni-metal. Oxidation of the fayalite component in olivine produced maghemite discs and cellular intergrowths with olivine and rare andradite-rich garnet. Cellular reactions require no long-range solid-state diffusion and are kinetically favourable during pyrometamorphic oxidation. Local melting of the cellular intergrowths resulted in three dimensional symplectic textures. Dynamic pyrometamorphism of this asteroidal particle occurred at approx. 1100 C during atmospheric entry flash (5-15 s) heating.

  6. 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 original amount of TiO2 incorporated in the olivine. Our measurements show maximum volume fraction of ilmenite of 1.21%, corresponding to 0.9±0.38 wt.% of TiO2. Even the most conservative scenario reveals concentration of TiO2 in olivine of more than 0.5 wt.%, a value comparable to that reported by Dobrzhinetskaya et al. (1996) and an order of magnitude greater than any previous measurement of TiO2 in olivine. Experiments by Dobrzhinetskaya et al. (Chem. Geol, 2000) found that such high solubility can occur, but only at P>10GPa at mantle temperatures.

  7. 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-clinopyroxene intergrowth. These features are inconsistent with "dry" olivine oxidation that is by the uptake of oxygen. Dehydrogenation of OH-bearing precursor olivine is suggested as a general mechanism of oxidation accompanied by chemical segregation and phase separation resulting in symplectite formation.

  8. Olivines in the Kaba carbonaceous chondrite and constraints on their formation

    NASA Technical Reports Server (NTRS)

    Hua, X.; Buseck, P. R.

    1993-01-01

    Kaba is unique in containing almost pure fayalitic olivine (Fo(sub 0.1)). Its coexistence with pure forsterite up to Fo(sub 99.6) and normal (Fo(sub 92) to Fo(sub 59)) and reversely (Fo(sub 0.4) to Fo(sub 4.7)) zoned olivines suggest that the Kaba olivines are in thermodynamic disequilibrium and experienced a complicated history. The fayalite is sufficiently pure that it is unlikely that it could have been produced by fractional crystallization. A gas-solid reaction under oxidizing conditions (H2O/H2 ratio approximately 10) is probably responsible for its formation.

  9. Fayalitic Olivine in Matrix of the Krymka LL3.1 Chondrite

    NASA Astrophysics Data System (ADS)

    Weisberg, M. K.; Zolensky, M. E.; Prinz, M.

    1995-09-01

    INTRODUCTION. Matrix persists as one of the most poorly characterized chondritic components. Its aggregational nature makes it an excellent place to search for primitive chondritic components that prevailed in the nebula during and after chondrule formation as well as components recording processes that predated and postdated accretion. In this study we focus on the occurrence and formation of the fayalitic olivine in the matrix of the Krymka LL3.1 unequilibrated ordinary chondrite. RESULTS. We limited our study to matrix areas clearly sandwiched between chondrules and did not include chondrule rims. In Krymka, matrix is coarser-grained and more Fe-rich than the rim material. Matrix is also highly variable in the size, shape and composition of its components, whereas chondrule rims appear more uniform. Krymka matrix is an aggregation of diverse mineral and lithic components. Mineral components include olivine, enstatite, diopsidic pyroxene, Ti-Al-rich Ca-pyroxene, hedenbergite, amorphous silicate material, spinel, oxides, troilite, and metal. Olivine is clearly dominant (~75% normative) and occurs in a variety of textures and compositions. Fayalitic olivine (Fa(sub)(58-94), avg.=Fa(sub)(72)) is ubiquitous throughout the matrix and occurs as (1) Isolated platelets (typically 1-3 micrometers x 3-5 micrometers, with some up to 10 micrometers in length), (2) Platelet clusters, which include randomly oriented platelets and/or intergrown platelets, (3) Platelet overgrowths which are overgrowths of parallel platelets on surfaces of larger (10-300 micrometers), more magnesian (Fa(sub)(4-34), avg.=Fa(sub)(19)) olivine fragments, (4) Euhedral-subhedral crystals (1-10 micrometers) which are often associated with and compositionally similar to platelets, and (5) Fluffy aggregates - irregularly shaped porous aggregates of submicron crystals. TEM study of the overgrowths reveals that the direction of elongation of the fayalitic platelets is along the c axis corresponding with the c direction of the larger olivine substrate. The larger, more magnesian olivine fragments are generally single crystals, but in some cases are associated with pyroxene (Fs(sub)(5-27),Wo(sub)(0.5-2)) or high-Ca pyroxene. These larger olivines are compositionally similar to chondrule olivines, whereas the fayalitic platelets are texturally and compositionally unlike olivines in chondrules. Fayalitic olivine with morphologies similar to those in Krymka matrix occur in the Chainpur LL3.4 and Ngawi LL3 matrix, but are much less common. These textures may have been characteristic of all primitive ordinary chondrite matrix, but were generally overprinted by metamorphic recrystallization. DISCUSSION: Fayalitic olivine in Krymka matrix records a process that has important implications for understanding the evolution of ordinary chondrites. It may form under oxidizing nebular conditions through solid state reactions in the presence of free silica, or vapor-solid reactions in a gas with a high silica activity [1,2]. Textural observations have been used to support a nebular origin for similar fayalitic olivine in CV3 matrix, and thermodynamic calculations indicate it could form in a nebula with a supersolar H2O/H2 ratio [3]. Vaporization experiments show that at ~10^(-6) bar and ~1650K olivine evaporates incongruently to produce a fayalitic vapor [4]. However, textural arguments favoring post-accretion formation of the fayalitic olivine in ordinary chondrite matrix and in CV3 dark inclusions have also been presented [5,6]. Thus, we consider three hypotheses for the formation of the fayalitic olivine in Krymka matrix: (1) vapor-solid reactions between a silica-rich vapor and metallic Fe degrees in the nebula, (2) vaporization of olivine-rich material to produce a fayalite vapor, followed by recondensation, or (3) parent body heating/dehydration of pre-existing phyllosilicates. Although the platy layered structure of some of the fayalitic olivine is suggestive of the layered structures of phyllosilicates and some fayalitic olivine texturally resembles saponite replacing olivine (as observed in the Kaidun CR chondrite), the platelet overgrowths on larger olivine crystals probably represent growth features and not a replacement of phyllosilicates. The platy morphology of fayalitic olivine could also indicate growth from a vapor consistent with hypotheses 1 and 2. The wide range in compositions of associated fayalitic olivine platelets suggests that they did not all form in the same environment and were not in contact under high enough temperatures to result in equilibrium; therefore, we conclude that the fayalitic olivine formed in a nebular environment. The fayalitic olivine platelets and associated fayalitic olivine in Krymka matrix may record vapor solid reactions under oxidizing nebular conditions or partial evaporation of a more Mg-rich olivine to produce a fayalite vapor, followed by recondensation. Formation through heating/dehydration of phyllosilicates is less likely. References. [1] Nagahara H. (1984) GCA, 48, 2581-2595. [2] Nagahara H. and Kushiro I. (1987) EPSL, 85, 537-547. [3] Hua X. and Buseck P. R. (1995) GCA, 59, 563-578. [4] Nagahara H. et al. (1994) GCA, 58, 1951-1963. [5] Alexander C. M. et al. (1989) EPSL, 95, 187-207. [6] Kojima T. and Tomeoka K. (1994) Meteoritics, 29, 484.

  10. An Olivine-Rich Crater in Tyrrhena Terra

    NASA Technical Reports Server (NTRS)

    2008-01-01

    This image of the ejecta of a crater in the Tyrrhena Terra region was taken by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) at 0328 UTC on February 23, 2007 (10:28 p.m. EST on February 22, 2007), near 13 degrees south latitude, 67 degrees east longitude. CRISM's image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 18 meters (60 feet) across. The region covered is roughly 9 kilometers (5.6 miles) wide at its narrowest point.

    Named for a classic albedo feature, Tyrrhena Terra is an extensive, heavily-cratered part of Mars' southern highlands, some 2,300 kilometers (1,430 miles) at its broadest extent. It is located to the northeast of the Hellas basin. The region imaged by CRISM is to the north of Hellas Planitia and just east of the crater Huygens in Tyrrhena Terra's western end.

    The uppermost image in the montage above reveals the location of the CRISM image on a mosaic taken by the Mars Odyssey spacecraft's Thermal Emission Imaging System (THEMIS). The CRISM image is located inside a large, flat-floored crater measuring about 52 kilometers (32 miles) across. The image includes a small crater and its ejecta blanket, an apron of material thrown out during a crater's formation, both located inside the larger crater.

    The lower left image is an infrared false-color image that reveals the extent of the ejecta blanket. It also includes ejecta from another small crater located just east of the CRISM image.

    The lower right image shows the strengths of mineral absorptions, and reveals the composition of the ejecta and surrounding material. The ejecta surrounding the small impact crater is thickest at the crater's rim, and becomes thinner to discontinuous at the blanket's outer edge. This small crater's ejecta blanket shows an enhanced spectral signature of the mineral olivine, as does the ejecta from the small crater just out of view to the east. In contrast the surrounding material is rich in the volcanic mineral pyroxene. This relationship demonstrates the layered characteristic of rocks forming the southern highlands: olivine-rich rock was buried by pyroxene-rich materials on the larger crater's floor, probably volcanic lavas. Later, the small crater penetrated the pyroxene-rich rock, excavated the underlying olivine-bearing unit, and deposited it as ejecta.

    CRISM is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, Laurel, Md., the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad. NASA's Jet Propulsion Laboratory, a division of the California Institute of Technology in Pasadena, manages the Mars Reconnaissance Orbiter and the Mars Science Laboratory for NASA's Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, built the orbiter.

  11. Olivine-metal mixtures: Spectral reflectance properties and application to asteroid reflectance spectra

    NASA Astrophysics Data System (ADS)

    Cloutis, Edward A.; Sanchez, Juan A.; Reddy, Vishnu; Gaffey, Michael J.; Binzel, Richard P.; Burbine, Thomas H.; Hardersen, Paul S.; Hiroi, Takahiro; Lucey, Paul G.; Sunshine, Jessica M.; Tait, Kimberly T.

    2015-05-01

    Olivine-rich asteroids appear to be common in the main asteroid belt as well as present in the near-Earth asteroid population. There are a number of meteorite classes that are dominated by olivine ± metal. To determine whether relationships exist between these asteroids and meteorites, we spectrally characterized a number of olivine + meteoritic metal powder intimate and areal mixtures, pallasite slabs, and olivine powders on a metal slab. Our goal is to understand the spectral characteristics of olivine + metal assemblages and develop spectral metrics that can be used to analyze reflectance spectra of olivine-dominated asteroids. We found that the major olivine absorption band in the 1 μm region is resolvable in intimate mixtures for metal abundances as high as ∼90 wt.%. The wavelength position of the 1 μm region olivine absorption band center is sensitive to Fa content but insensitive to other variables. However, the band minimum position moves to shorter wavelengths with increasing metal abundance due to changes in spectral slope. The full width at half maximum (FWHM) of this band and reflectance at 1.8 μm are both most sensitive to olivine Fa content, metal abundance, and grain size, and much less to the presence of nanophase iron that reddens spectra. Reflectance at 0.56 μm and the 1.8/0.56 μm reflectance ratio are sensitive to these same parameters as well as to nanophase iron-associated spectral reddening. The wavelength position of the local reflectance maximum in the 0.7 μm region moves to longer wavelengths with increasing metal abundance and is most useful for constraining metal abundance in high metal-content mixtures. Pallasite slab spectra differ in a number of respects from powdered assemblages and multiple spectral parameters can be used to discriminate them. The spectra of increasingly fine-grained olivine + metal assemblages and those involving low-Fa olivine show increasing spectral dominance by metal. Systematic application of multiple spectral metrics allows olivine + metal assemblage properties such as Fa content, olivine/metal ratio, and grain size to be quantified or constrained. Analysis of reflectance spectra of 22 presumed olivine ± metal-rich asteroids indicates that most of them possess low- to medium-Fa content olivine (Fa<∼67), with variable abundances of macroscopic metal. A number exhibit visible region absorption bands that are indicative of some fraction of coarser-grained olivine (>45 μm). Most asteroid spectra can be plausibly linked to specific olivine ± metal-bearing meteorite classes. Most of the asteroid spectra examined exhibit some degree of spectral reddening below ∼1.8 μm which is most consistent with the presence of fine-grained nanophase iron, likely produced by space weathering.

  12. 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 ?m-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 ?m 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 0.8 wt% to 2.5 wt% H2O. From experimental data for Fo83, Fo87, Fo90 and Fo100 compositions we calculate mineral-specific absorption coefficients for the quantification of H2O using IR-spectroscopy, compare them with previously estimated values and discuss IR calibrations for major phases of the Earth's mantle.

  13. 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 decades ago but now is proved further by our result. Therefore, our study is not only instructive for realizing the dynamic process of slab subduction, but also helpful for analyzing the mechanism of deep earthquakes.

  14. Reactive flow as dominant evolution process in the lowermost oceanic crust: evidence from olivine of the Pineto ophiolite (Corsica)

    NASA Astrophysics Data System (ADS)

    Sanfilippo, Alessio; Tribuzio, Riccardo; Tiepolo, Massimo; Berno, Davide

    2015-10-01

    The Jurassic Pineto ophiolite from Corsica exposes a ~1-km-thick troctolite-olivine-gabbro sequence, interpreted to represent a lowermost sector of the gabbroic oceanic crust from a (ultra-)slow spreading system. To constrain the petrogenesis of the olivine-gabbros, minor and trace element analyses of olivine (forsterite = 84-82 mol%) were carried out. Olivine from the olivine-gabbros is depleted in incompatible trace elements (Sc, V, Ti, Y, Zr and heavy rare earth elements) with respect to olivines from associated troctolites. Depleted incompatible element compositions are also shown by olivine (forsterite = 86 mol%) from a clinopyroxene-rich troctolite. The incompatible element compositions of olivine argue against a petrogenetic process entirely driven by fractional crystallization. We propose that melts migrating through an olivine-plagioclase crystal mush chemically evolved by reaction with the existing minerals, changing in composition as it flowed upward. The melt residual from these interactions led to partial dissolution of preexisting olivine and to crystallization of clinopyroxene, generating olivine-gabbro bodies within a troctolite matrix. Reactive flow was the major evolution process active in the ~1-km crustal transect exposed at the Pineto ophiolite, producing lithological variations classically attributed to fractional crystallization processes.

  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. 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.

  17. Fayalitic olivine in matrix of the Krymka LL3.1 chondrite: Vapor-solid growth in the solar nebula

    NASA Astrophysics Data System (ADS)

    Weisberg, Michael K.; Zolensky, Michael E.; Prinz, Martin

    1997-11-01

    Fayalitic olivine (Fa54-94) is a ubiquitous component in the matrix of Krymka (LL3.1) as well as in other highly unequilibrated chondrites (ordinary and carbonaceous). In Krymka, the fayalitic olivine has an unusual anisotropic platy morphology that occurs in at least five types of textural settings, which can be characterized as: (1) isolated platelets, (2) clusters of platelets, (3) euhedral to subhedral crystals, (4) overgrowths of platelets on forsteritic olivine, and (5) fluffy (porous) aggregates. From TEM investigation, the direction of elongation of the platy olivine overgrowths on forsteritic olivine substrates is along the c axis and in most cases it corresponds with the c axis of the substrate olivine, suggesting that the fayalitic olivine grew in this unusual morphology and is not a replacement product of preexisting material. The fayalitic olivine in the matrix of Krymka is compositionally similar to olivine with platy morphology in the matrix of some CV3 chondrites and both have similar Fe/Mn ratios, but important morphological differences indicate that their relationship needs to be explored further. Textural and compositional data indicate that the fayalitic olivine in the matrix of Krymka, as well as in some other unequilibrated ordinary chondrites, formed prior to final lithification of the meteorite and probably prior to parent body accretion. We find that formation of the fayalitic olivine by vapor-solid growth provides the best explanation to our observations and data, and is the only feasible mechanism for the formation of fayalitic olivine in the matrix of Krymka. We propose that the fayalitic olivine formed by vaporization and recondensation of olivine rich-dust, during a period of enhanced dust/gas ratio in the nebula.

  18. 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.

  19. 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

  20. 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.

  1. Excitation and relaxation of olivine after swift heavy ion impact

    NASA Astrophysics Data System (ADS)

    Gorbunov, S. A.; Medvedev, N. A.; Rymzhanov, R. A.; Terekhin, P. N.; Volkov, A. E.

    2014-05-01

    A multiscale model was developed to describe excitation and initial relaxation of an insulator after an impact of a swift heavy ion (SHI) decelerated in the electronic stopping regime. This model consists of a combination of three methods: (a) Monte Carlo simulations of the nonequilibrium kinetics of the electron subsystem of a solid at the femtosecond scale after the projectile passage. The complex dielectric function (CDF) is used to construct the cross sections for the MC model taking into account a collective response of the electron ensemble to excitation. (b) A molecular-kinetic approach describing further spatial spreading of electrons after finishing of ionization cascades up to hundred femtoseconds. And (c) molecular dynamics simulations of a reaction of the lattice on the excess energy transferred from the relaxing electron subsystem at the picosecond time scale. The dynamic structure factor (DSF) formalism is used to calculate the electron-lattice energy exchange in a general way which is valid for sub-picosecond timescales, beyond the phononic approximation of the lattice dynamics. The calculations were performed for 2 GeV Au ion in olivine, demonstrating a heating of the lattice up to 700 K in the nanometric scale picoseconds after the projectile passage.

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

    NASA Technical Reports Server (NTRS)

    King, Trude V. V.; Ridley, W. Ian

    1987-01-01

    High-resolution visible and near-IR diffuse spectral reflectance are used to systematically investigate apparent wavelength shifts as a function of mineral chemistry in the Fe/Mg olivine series from Fo(11) to Fo(91). The study also shows that trace amounts of nickel can be spectrally detected in the olivine structure. Significant compositional information can only be extracted at relatively high resolution, because the overall spectral characteristics of the olivines change only subtly as a function of the Fe/Mg ratio. This laboratory study is expected to aid in the interpretation of remotely sensed data from both terrestrial and extraterrestrial bodies. Terrestrial applications may include the recognition of ultramafic, ultrabasic, and basaltic terrains which in themselves may have mineral potential. Among extraterrestrial applications, the asteroids are obvious candidates for further examination. Some permutations of Fe-Mg-Ni relations in olivines are discussed as they apply to the interpretation of asteroid surfaces and other extraterrestrial bodies.

  3. 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.

  4. Optical constants of olivine particles between wavelengths of 7 and 200 microns

    SciTech Connect

    Mukai, Tadashi; Koike, Chiyoe Kyoto Pharmaceutical Univ. )

    1990-09-01

    Emission features are computed for spherical olivine particles of 0.03, 0.3, 3.0, and 30 micron radii, on the basis of laboratory determinations of the olivine particles' optical constants over the 7 to 200 micron range. It is noted that, while particles of radii smaller than 0.3 microns exhibit emission peaks at 16.3, 18.6, 23, 28, and 33.6 microns, together with a 10-micron region twin-peak structure, these readings weaken for particle radii of 3 microns or more. The appearance of the twin-peak feature in Comet P/Halley is accordingly judged to imply the presence of olivine particles smaller than 1 micron in radius; alternatively, such smaller olivines' enhancement may occur in the comet, which also exhibits a 10-micron silicate band twin-peak feature. 26 refs.

  5. 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)

  6. 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.

  7. 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.

  8. Palisades sill: Origin of the olivine zone by separate magmatic injection rather than gravity settling

    SciTech Connect

    Husch, J.M. )

    1990-08-01

    The still widely cited view of the Palisades sill, northeastern United States, being differentiated largely by vertically directed olivine-dominated frationation is not supported by available structural, petrographic, and geochemical data. Rather, the sill can be viewed as a sheetlike composite intrusion, possibly made up of multiple magma types common to the Mesozoic eastern North America magmatic province. The famous olivine zone of the Palisades sill may have resulted from a separate late intrusion of olivine-normative magma and not from gravity-controlled, olivine-accumulation processes. Pyroxene-dominated fractionation accounts for much of the vertical and lateral compositional variations in the Palisades sill and other related intrusions from the province.

  9. Palisades sill: Origin of the olivine zone by separate magmatic injection rather than gravity settling

    NASA Astrophysics Data System (ADS)

    Husch, Jonathan M.

    1990-08-01

    The still widely cited view of the Palisades sill, northeastern United States, being differentiated largely by vertically directed, olivine-dominated fractionation is not supported by available structural, petrographic, and geochemical data. Rather, the sill can be viewed as a sheetlike composite intrusion, possibly made up of multiple magma types common to the Mesozoic eastern North America magmatic province. The famous olivine zone of the Palisades sill may have resulted from a separate late intrusion of olivine-normative magma and not from gravity-controlled, olivine-accumulation processes. Pyroxene-dominated fractionation accounts for much of the vertical and lateral compositional variations in the Palisades sill and other related intrusions from the province.

  10. 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).

  11. Olivine-rich exposures in the South Pole-Aitken Basin

    NASA Astrophysics Data System (ADS)

    Yamamoto, Satoru; Nakamura, Ryosuke; Matsunaga, Tsuneo; Ogawa, Yoshiko; Ishihara, Yoshiaki; Morota, Tomokatsu; Hirata, Naru; Ohtake, Makiko; Hiroi, Takahiro; Yokota, Yasuhiro; Haruyama, Junichi

    2012-03-01

    The distribution and the geological context of the olivine-rich exposures in the South Pole-Aitken (SPA) Basin on the Moon were investigated based on the spectral data obtained from the Spectral Profiler (SP) and Multiband Imager (MI) onboard the Japanese lunar explorer Kaguya/SELENE. The olivine-rich exposures are found only in the peak rings or central peaks of the Schrödinger basin and Zeeman crater, which are located in the outer region of the SPA Basin and not in the center region. On a localized scale, the olivine-rich materials are exposed on landslide features on the crater walls or sloped wall of the central peaks or the peak rings. Another observational finding is the co-existence of olivine-rich and plagioclase-rich materials on a kilometer scale spanning most of the olivine-rich sites in the Schrödinger basin. Pyroxene-rich materials are found in fresh craters outside the peak rings or the central peaks with olivine-rich materials. Based on these results, the following scenario are proposed: (1) the impact to form the SPA Basin melted a large amount of the lunar upper mantle and crust, and distributed the melted materials to the outer region; (2) local differentiation of melted materials hid the olivine-rich materials in the center region of the SPA Basin; (3) later impacts that formed the Schrödinger and Zeeman craters excavated and exposed the olivine-rich materials to the surface again; and (4) space weathering and regolith gardening obscured the olivine-rich spectra at the exposure sites, but recent, small scale impacts or landslides on the sloped wall exposed fresh olivine-rich materials, allowing the identification of the olivine-rich exposures by spectral remote-sensing. This suggests that several, different scale events play an important role in forming the surface distributions of originally deep-seated materials on the Moon, as well as on other planetary bodies.

  12. 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.

  13. A Tale of Two Olivines: Magma Ascent in the Auckland Volcanic Field, New Zealand

    NASA Astrophysics Data System (ADS)

    Smid, E. R.; McGee, L. E.; Smith, I. E.; Lindsay, J. M.

    2013-12-01

    The Auckland Volcanic Field (AVF) is a nephelinitic to subalkali basaltic monogenetic field centered on the city of Auckland, New Zealand. Lavas are olivine-phyric, and the deposits of several volcanoes in the field contain olivine crystals with chrome spinel (Cr-spinel) inclusions. Microprobe analyses show at least two populations of olivine, categorised by their Mg# and their spinel inclusion compositions: the first has olivines that are euhedral, have compositions slightly less forsteritic than expected for whole rock Mg#, and have Cr-spinel inclusions with relatively low Cr2O3 contents of ~20%. These are interpreted as antecrysts inherited from the mantle source that yielded their host magma. The second population is characterised by olivines that are sub- to euhedral, are significantly more forsteritic than expected from their host whole rock Mg#, and have Cr-spinel inclusons with relatively high Cr2O3 contents of ~50%. These are interpreted as xenocrysts. The composition of these high Cr2O3 spinels very closely resembles the composition of spinels within olivines in dunite sampled from the Dun Mountain Ophiolite on the South Island of New Zealand. The northward extension of the Dun Mountain complex beneath the North Island is defined by the Junction Magnetic Anomaly, marking a crustal terrane boundary that underlies the Auckland Volcanic Field. These data indicate that the magmas that have risen to produce the volcanoes of the Auckland Volcanic Field have carried crystals from an underlying ultramafic crust as well as from their asthenospheric source. Euhedral olivine crystals which do not contain Cr-spinel are also present in AVF lavas and these are interpreted as true phenocrysts that crystallised directly from their host magmas. The lack of reaction textures at crystal margins suggests rapid ascent rates. A crustal origin for the xenocrysts not only has large implications for ascent rate modelling of olivines, but also for the crustal structure of the Auckland area and possible magma ascent paths under the AVF.

  14. 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.

  15. 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.

  16. Disclinations provide the missing mechanism for deforming olivine-rich rocks in the mantle.

    PubMed

    Cordier, Patrick; Demouchy, Sylvie; Beausir, Benoît; Taupin, Vincent; Barou, Fabrice; Fressengeas, Claude

    2014-03-01

    Mantle flow involves large strains of polymineral aggregates. The strongly anisotropic plastic response of each individual grain in the aggregate results from the interactions between neighbouring grains and the continuity of material displacement across the grain boundaries. Orthorhombic olivine, which is the dominant mineral phase of the Earth's upper mantle, does not exhibit enough slip systems to accommodate a general deformation state by intracrystalline slip without inducing damage. Here we show that a more general description of the deformation process that includes the motion of rotational defects referred to as disclinations can solve the olivine deformation paradox. We use high-resolution electron backscattering diffraction (EBSD) maps of deformed olivine aggregates to resolve the disclinations. The disclinations are found to decorate grain boundaries in olivine samples deformed experimentally and in nature. We present a disclination-based model of a high-angle tilt boundary in olivine, which demonstrates that an applied shear induces grain-boundary migration through disclination motion. This new approach clarifies grain-boundary-mediated plasticity in polycrystalline aggregates. By providing the missing mechanism for describing plastic flow in olivine, this work will permit multiscale modelling of the rheology of the upper mantle, from the atomic scale to the scale of the flow. PMID:24572356

  17. Geochemistry and origin of metal, olivine clasts, and matrix in the Dong Ujimqin Qi mesosiderite

    NASA Astrophysics Data System (ADS)

    Kong, Ping; Su, Wen; Li, Xianhua; Spettel, Bernhard; Palme, Herbert; Tao, Kejie

    2008-03-01

    The Dong Ujimqin Qi mesosiderite is the first recorded fall of a stony-iron meteorite in China. According to silicate textures and metal composition, this meteorite is classified as a member of subgroup IB. Instrumental neutron activation analyses (INAA) of metals show that the matrix metal has lower concentrations of Os, Ir, Re, and Pt, but higher concentrations of Ni and Au than the 7.5 cm metal nodule present in the meteorite. We attribute these compositional differences to fractional crystallization of molten metal. Studies of olivine clasts show that FeO contents are uniform in individual olivine crystals but are variable for different olivine clasts. Although concentrations of rare earth elements (REEs) change within olivine clasts, they all exhibit a vee-shaped pattern relative to CI chondrites. The relatively high concentrations of REEs in olivine and the shape of REE patterns require a liquid high in REEs and especially in light REEs. As such a liquid was absent from the region where basaltic and gabbroic clasts formed, mesosiderite olivine must have formed in a part of the differentiated asteroid that is different from the location where other mesosiderite silicate clasts formed.

  18. 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.

  19. 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 lithified.

  20. 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 ranged from tens to a few microns with textures that remained relatively sharp and were crystallographically controlled. These results were comparable to that observed in the "naturally" weathered comparison/reference grains. Chemical analysis by EDS indicates these textures correlated with the relative loss of Mg and Fe cations by diffusional processes. In contrast the biotic results indicated changes in the etching patterns on the scale of hundreds of nm, which are neither sharp nor crystallographically controlled (nanoetching). Organisms, organic debris and/or extracellular polymeric substances (biofilm) were often in close proximity or direct contact with the nanoetching. While there are many poorly constrained variables in natural weathering experiments to contend with, such as the time scale, the chemistry of the fluids and degree of biologic participation, some preliminary observations can be made: (1) certain distinct surface textures appear correlated with the specific processes giving rise to these textures; (2) the process of diffusing cations can produce many similar styles of surface textural changes; and (3) the main difference between abiotic and biotically produced weathering is the scale (microns versus nanometers) and the style (crystallographically versus noncrystallographically controlled) of the textural features. Further investigation into nanosize scale surface textures should attempt to quantify both textures and chemical changes of the role of microorganisms in the weathering of silicates. Additional experiments addressing nanoscale textures of shock features for comparison with the current data set.

  1. Calculations of Li Ion Diffusion in Olivine Phosphates

    SciTech Connect

    Dathar, Gopi Krishna Phani; Sheppard, Daniel; Stevenson, Keith J.; Henkelman, Graeme

    2011-09-13

    Kinetic pathways of Li-ion diffusion in olivine phosphates are calculated from density functional theory (DFT). Previously reported theoretical diffusion rates for Li ions and vacancies in defect-free crystalline FePO₄ and LiFePO₄ are six orders of magnitude faster than experimentally measured values. This discrepancy can be resolved by considering the different components of Li kinetics, including diffusion in the bulk, on the surface, in the presence of defects, and in varying local environments. Using DFT+U, we quantify each of these effects and determine that, while bulk diffusion is affected by strain and Li concentration, these are not significant enough to explain the slow diffusion observed in experiment. However, surface diffusion is observed to have have high barriers, which could contribute to slow kinetics in nanostructured cathodes. Anti-site defects also provide a possible explanation for slow diffusion, but only for vacancy diffusion in LiFePO₄, which has a barrier of 0.71 eV, compared to 0.29 eV in defect-free channels. In FePO₄, a concerted Li-ion diffusion mechanism around the anti-site defect is found to have a low barrier of 0.35 eV, allowing for facile cross-channel diffusion at room temperature. The difference between Li-ion and vacancy diffusion is understood in terms of a favorable coordination between Li ions and localized electrons on Fe centers at the transition states for Li-ion hopping in FePO₄. Greater distances between vacancies and holes at the transition states for vacancy diffusion lead to higher diffusion barriers.

  2. Laboratory measurements of the viscous anisotropy of olivine aggregates.

    PubMed

    Hansen, L N; Zimmerman, M E; Kohlstedt, D L

    2012-12-20

    A marked anisotropy in viscosity develops in Earth's mantle as deformation strongly aligns the crystallographic axes of the individual grains that comprise the rocks. On the basis of geodynamic simulations, processes significantly affected by viscous anisotropy include post-glacial rebound, foundering of lithosphere and melt production above subduction zones. However, an estimate of the magnitude of viscous anisotropy based on the results of deformation experiments on single crystals differs by three orders of magnitude from that obtained by grain-scale numerical models of deforming aggregates with strong crystallographic alignment. Complicating matters, recent experiments indicate that deformation of the uppermost mantle is dominated by dislocation-accommodated grain-boundary sliding, a mechanism not activated in experiments on single crystals and not included in numerical models. Here, using direct measurements of the viscous anisotropy of highly deformed polycrystalline olivine, we demonstrate a significant directional dependence of viscosity. Specifically, shear viscosities measured in high-strain torsion experiments are 15 times smaller than normal viscosities measured in subsequent tension tests performed parallel to the torsion axis. This anisotropy is approximately an order of magnitude larger than that predicted by grain-scale simulations. These results indicate that dislocation-accommodated grain-boundary sliding produces an appreciable anisotropy in rock viscosity. We propose that crystallographic alignment imparts viscous anisotropy because the rate of deformation is limited by the movement of dislocations through the interiors of the crystallographically aligned grains. The maximum degree of anisotropy is reached at geologically low shear strain (of about ten) such that deforming regions of the upper mantle will exhibit significant viscous anisotropy. PMID:23257885

  3. Experimental Partitioning of Cr(3+) and Sc(3+) into Olivine: Mechanisms and Implications

    NASA Technical Reports Server (NTRS)

    Jones, John; Mackwell, S. J.

    2006-01-01

    Olivine (Mg, Fe)Si2O4 does not, by stoichiometry, accept cations such as Sc(3+) or Cr(3+). However, the partition coefficients of Sc and Cr between olivine and liquid are significant 0.2-1.0. We have measured Cr(3+) partition coefficients of near unity and have grown olivines with nearly 3 wt.% Sc2O3. Therefore, there must be a simple means of charge balancing 3+ ions in a crystal structure that was obviously not designed to receive other than 2+ ions on the olivine M sites. The simplest explanation is that two 3+ ions enter the olivine structure by displacing three 2+ ions and creating an M site vacancy. Even this explanation has difficulties. For minor elements in our experiments (1 wt.%) the odds of a minor element 3+ ion finding a second 3+ for charge balance are of the order of 100:1 against. Because of the reducing conditions of our experiments, Fe(3+) will not suffice; and Al(3+) is not in sufficient quantity in olivine for charge balance. Therefore, Cr or Sc must, in effect, charge balance itself. For true trace elements, the problem is compounded many times. For an ion at the 10 ppm level the chances of finding a second (for example) Sc ion is approx.10(exp 5):1 against. Of course, any other 3+ ion would suffice but comparisons between percent level doping experiments and trace level partitioning indicate that Henry s law is obeyed. This implies that the same substitution mechanism occurs at both the percent and tens of ppm levels. There are two simple solutions to this problem: (i) The electrical conductivity of olivine is such that charge balance need not be local. This requires substantial domains within the olivine crystal in electrical contact by migration of vacancies or electronic defects. (ii) The 3+ cation brings along its own charge-balancing ion because it existed as a dimer in the silicate liquid. Olivine is not a true insulator but is actually a p-type semiconductor. Even so, electrical communication by this means is unlikely over the tens or hundreds of unit cells that would be required for charge balance to be local. Therefore, we cautiously favor the idea that melt speciation is the means by which 3+ ions enter the olivine structure. Possibly this model might be tested by in situ XAFS measurements or by molecular dynamical calculations.

  4. Role of olivine cumulates in destabilizing the flanks of Hawaiian volcanoes

    USGS Publications Warehouse

    Clague, D.A.; Denlinger, R.P.

    1994-01-01

    The south flank of Kilauea Volcano is unstable and has the structure of a huge landslide; it is one of at least 17 enormous catastrophic landslides shed from the Hawaiian Islands. Mechanisms previously proposed for movement of the south flank invoke slip of the volcanic pile over seafloor sediments. Slip on a low friction de??collement alone cannot explain why the thickest and widest sector of the flank moves more rapidly than the rest, or why this section contains a 300 km3 aseismic volume above the seismically defined de??collement. It is proposed that this aseismic volume, adjacent to the caldera in the direction of flank slip, consists of olivine cumulates that creep outward, pushing the south flank seawards. Average primary Kilauea tholeiitic magma contains about 16.5 wt.% MgO compared with an average 10 wt.% MgO for erupted subaerial and submarine basalts. This difference requires fractionation of 17 wt.% (14 vol.%) olivine phenocrysts that accumulate near the base of the magma reservoir where they form cumulates. Submarine-erupted Kilauea lavas contain abundant deformed olivine xenocrysts derived from these cumulates. Deformed dunite formed during the tholeiitic shield stage is also erupted as xenoliths in subsequent alkalic lavas. The deformation structures in olivine xenocrysts suggest that the cumulus olivine was densely packed, probably with as little as 5-10 vol.% intercumulus liquid, before entrainment of the xenocrysts. The olivine cumulates were at magmatic temperatures (>1100??C) when the xenocrysts were entrained. Olivine at 1100??C has a rheology similar to ice, and the olivine cumulates should flow down and away from the summit of the volcano. Flow of the olivine cumulates places constant pressure on the unbuttressed seaward flank, leading to an extensional region that localizes deep intrusions behind the flank; these intrusions add to the seaward push. This mechanism ties the source of gravitational instability to the caldera complex and deep rift systems and, therefore, limits catastrophic sector failure of Hawaiian volcanoes to their active growth phase, when the core of olivine cumulates is still hot enough to flow. ?? 1994 Springer-Verlag.

  5. 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.

  6. Single-Crystal Elasticity of San Carlos Olivine in the Earth's Mantle

    NASA Astrophysics Data System (ADS)

    Mao, Z.; Lin, J.; Fan, D.; Yang, J.; Zhuravlev, K. K.; Tkachev, S. N.

    2013-12-01

    Based on the pyrolitic compositional model, olivine is the most abundant mineral in the Earth's upper mantle. Experimental and theoretical studies on physical, chemical, and transport properties of olivine have attracted extensive research interests over last decades and have greatly contributed to our understanding on the structure and composition of the Earth's upper mantle. Single-crystal elasticity of olivine at relevant pressure-temperature conditions is of particular importance in constraining the composition, interpreting the observed anisotropy, and understanding the seismic tomography and heterogeneity of the region. However, single-crystal elasticity of olivine has never been investigated at simultaneous high pressure-temperature conditions of the upper mantle. Much of our current knowledge on the velocity structures of the upper-mantle minerals heavily relies on extrapolations of limited mineral physics results. In this study, we have studied single-crystal elasticity of San Carlos olivine [(Mg0.9Fe0.1)2SiO4] up to 16 GPa and 750 K using Brillouin spectroscopy and X-ray diffraction in an externally-heated diamond anvil cell. We have derived full elastic tensors of the olivine at high pressure-temperature conditions, providing crucial constraints on the combined effects of pressure and temperature on the single-crystal elasticity of olivine. These results have been applied to model the velocity structures and seismic Vp/Vs anisotropies of the Earth's upper mantle and olivne mantle wedge in the subduction are by combing with literature deformation results. Here we will present these results to address current outstanding issues in the geophysics, geochemistry, and seismology of the upper mantle.

  7. 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.

  8. 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.

  9. Effect of fO2 on the incorporation and diffusivity of Li in olivine

    NASA Astrophysics Data System (ADS)

    Dohmen, R.; Coogan, L. A.

    2012-12-01

    Over the last decade the geochemical behaviour of Li has become of special interest since it was speculated that Li stable isotopes could be a promising tracer for subduction zone processes. However, there have been many studies of natural samples but our experimental and theoretical basis for interpreting these data is still lacking. Two diffusion mechanisms were identified for Li in olivine [1]. Their contribution to the net flux of Li in olivine depends on the vacancy concentration on the metal sites, which is sensitive to the fO2. Therefore we have studied the effect of fO2 on Li solubility and diffusion in olivine. Experimental approach: thin plates of crushed, natural olivine single crystals were embedded into two different kind of powders, ground plagioclase with about 2.5 ppm Li or a pre-annealed powder mixture of San Carlos olivine and isotopically enriched Li. All runs were performed in a gas-mixing furnace with fO2 controlled by flowing CO/CO2 mixture. In each run we simultaneously annealed about 100 micrometer-sized samples of Pakistan olivine and San Carlos olivine. In addition we have added to each run a mm sized crystallographically oriented parallelepiped of San Carlos olivine. For each powder reservoir we have performed a set of three anneals at 1200 C and different fO2. Cross sections of the run products were polished and analyzed with LA-ICP-MS. Results: In all cases the Li isotopes and concentrations were homogeneous in the 100 micrometer sized grains with one exception, the experiment at 1.e-10 bar with the highly enriched Li reservoir. The final Li concentration was slightly lower in the Pakistan than San Carlos olivine and was much lower in general if buffered by the plagioclase powder. Most importantly, the Li concentration increased systematically with increasing oxygen fugacity, indicating that the incorporation of Li in olivine is fO2 dependent. The mm-sized, oriented crystal was in most cases zoned and the extent of zoning depends on the diffusion direction. In addition the profiles became systematically longer with decreasing fugacity and at the most reducing conditions the crystal was almost homogenous. However, the isotopes were in all cases completely homogenized and equilibrated with the isotopically enriched reservoir. Thermodynamic model: We extended the quantitative point defect model for olivine [2] and reproduced the effect of fO2 on the solubility of Li when we assume it is mainly on the metal site and charge balanced by the formation of Fe3+ on the metal site. Conclusions: Our results strongly indicate that incorporation of Li is dependent on the fO2, less dependent on the trace element content. Diffusion of Li in olivine is anisotropic and dependent on fO2. Our quantitative point defect model for olivine underpins the experimental results. This will allow us to develop a multi-component diffusion model considering relevant point defects, e.g. Fe3+ and metal vacancies. Such a model will hopefully help us to simulate diffusion of Li at various natural circumstances including fO2 as a critical parameter. References: [1] Dohmen et al. (2010) Geochim Cosmochim Acta 74, 274-292; [2] Dohmen and Chakraborty (2007), Phys Chem Minerals 34, 597- 598.

  10. Granoblastic olivine aggregates in magnesian chondrules: Planetesimal fragments or thermally annealed solar nebula condensates?

    NASA Astrophysics Data System (ADS)

    Whattam, Scott A.; Hewins, Roger H.; Cohen, Bosmat A.; Seaton, Nicholas C.; Prior, David J.

    2008-05-01

    Granoblastic olivine aggregates (GOA) have been discovered in some Type I magnesian chondrules within carbonaceous chondrites by Libourel and Krot [Libourel, G., Krot, A.N., 2007. Evidence for the presence of planetesimal material among the precursors of magnesian chondrules of nebular origin. Earth Planet. Sci. Lett. 254, 1-8], who proposed an origin from pre-existing planetesimals. Amoeboid olivine aggregates (AOA), generally considered as aggregates of solar nebula condensates and found within similar carbonaceous chondrites, display similar equilibrium texture, though on a finer scale. For these reasons, we conducted experiments to determine if annealing of olivine required time scales appropriate to planetesimal or nebular heating. Pressed < 43 µm and < 63 µm San Carlos olivine powder (Fo 88.4) was isothermally heated at temperatures ranging from 1350-1550 °C for 1-100 h. The 100 h runs yield olivine aggregates with well-developed granoblastic texture at all temperatures, manifest as a network of randomly-oriented and sutured olivine grains with 120° triple junctions. Individual olivine grains are 4-6 sided and polygonal by 1450 °C and equigranular texture is developed at high temperature (1500-1550 °C). Melting of olivine commences at 1450-1500 °C and aids in 'ripening' and suturing (grain coarsening and grain boundary migration). Textural equilibrium is clearly met at 1550 °C. A planetesimal origin cannot be ruled out; however, the experimental evidence reveals that granoblastic texture can be reproduced in an interval not inconsistent with heating times for nebular objects. GOA may have experienced higher degrees of thermal processing than the finer-grained AOA. If the precursors were the same, grain coarsening would have to be accompanied by modification to bulk and isotopic compositions. However, the precursors could have been olivine condensates formed later than AOA. Annealing may have been a widespread process operating in the primordial solar nebula responsible for thermal processing and formation of GOA prior to their incorporation into chondrules.

  11. 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.

  12. 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 shipping capacity of tankers and bulk carriers is entirely used for olivine dissolution ten times a year. Reference Köhler, P.; Hartmann, J. and Wolf-Gladrow, D. A. (2010) Geoengineering potential of artificially enhanced silicate weathering of olivine, Proceedings of the National Academy of Science 107, 20228-20233, doi: 10.1073/pnas.1000545107.

  13. Modal mineralogy of the surface of Vesta: Evidence for ubiquitous olivine and identification of meteorite analogue

    NASA Astrophysics Data System (ADS)

    Poulet, F.; Ruesch, O.; Langevin, Y.; Hiesinger, H.

    2015-06-01

    The observations of the surface of 4 Vesta by the Visible and Infrared Mapping Spectrometer (VIR) onboard the Dawn spacecraft reveals that its composition is dominated by pyroxenes with olivine in very localized spots. To derive new constraints on the surface composition of the asteroid, we apply a scattering model to VIR reflectance spectra. The model is first calibrated by performing a non-linear deconvolution of laboratory spectra of mineral mixtures and howardite, eucrite, diogenite (HED) meteorites. Abundance estimates of minerals are accurate to within 15-25% for the analyzed samples, while the estimated particle sizes are within the intervals of actual sizes. Grain size effects complicate spectral deconvolution and estimation of modal abundances of samples (both HED and mineral mixtures) that contain olivine. The magnesium-rich olivine detection threshold is 10-20% for large grain sizes (100s μm) and several 10s% for small grain sizes (<50 μm). Major expected minerals (low-calcium pyroxenes, high-calcium pyroxenes, plagioclase and olivine) can provide satisfactory fits of VIR spectra with excellent residuals ⩽1%. Terrains with the strongest low-calcium pyroxene signatures are well representative of diogenites. The best fits of any unit are obtained by including Fo70 olivine at an abundance level of 10-20%, with an uncertainty of ∼10%. Olivine is therefore likely to be ubiquitous over the whole surface of Vesta. Olivine is coarser grained (a few hundred μm) than other minerals such as orthopyroxene and clinopyroxene (grain sizes typically smaller than 100 μm). Both the grain size variance and the modal mineralogy are consistent with the lithologic size and mineral distributions of howardites containing olivine phenocryst-bearing melt. These howardites are the best petrologic analogues of Vesta. Such a surface assemblage could be the result of successive melting and mixing processes due to impacts. The compositional view confirms that Vesta underwent major homogenization processes, resulting in a relatively uniform modal mineralogy and explaining the lack of specific olivine enrichment in the Rheasilvia ejecta.

  14. Space Weathering in Olivine and the Mineralogy of (Some) M-Class Asteroids

    NASA Astrophysics Data System (ADS)

    Britt, Daniel; Kohout, Tomas; Schelling, Patrick; Consolmagno, Guy J.

    2014-11-01

    One aspect of space weathering of airless bodies is the production of nanophase iron (npFe0) from Fe bearing silicate minerals. The combined effects of low oxygen fugacity and solar-wind implanted H tend to result in strongly-reduced surfaces that can be chemically activated by heating due to micrometeorite impacts. The mineral kinetics of olivine makes it particularly vulnerable to reduction, decomposition, and npFe0 production. Kohout et al. has recently developed a new method of controlled npFe0 production on olivine powder grains that mimics the essential features of this weathering process and was developed to quantitatively evaluate spectral changes related to space weathering and presence of npFe0. Compared to fresh olivine the treated samples exhibit spectral characteristics of space weathering including spectral darkening, shallowing and attenuation of 1 µm olivine absorption band, and reddening. The attenuation of the 1 µm band significantly shrinks the band FWHM and shifts the much reduced band center to shorter wavelengths around 0.95 µm. These spectral changes are related to increasing amounts of npFe0 and the disruption of the crystal structure of the parent olivine. Significantly, the darkened, reddened, and band attenuated olivine spectra are a close match to a number of M-class asteroids. What is particularly interesting is the match with the weak absorption band near 0.95 µm seen in many M-class asteroids (i.e. 16 Psyche, 22 Kalliope, 55 Pandora to name a few). One of the major issues in asteroid science is the relative scarcity of olivine asteroids (the ”Great Dunite Shortage” coined by Bell et al in Asteroids II). One possibility worth further study is that asteroidal olivine may be hidden by the relative ease with which it weathers. The surface chemical and micrometeorite environment in the asteroid belt may produce over time a spectrum for an olivine-rich surface that is remarkably similar to that of an M-class asteroid.

  15. 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-class sulfide ore body that is loaded with olivine crystals-the Jinchuan ore body, China, and provides a reasonable, alternative explanation for sulfide formation and deposition.

  16. Electron microscope study of the stability field and degree of nonstoichiometry in olivine

    SciTech Connect

    Boland, J.N.; Duba, A.G.

    1986-04-10

    The stability of San Carlos olivine (Fo 90.5) relative to changes in oxygen fugacity at 1300 /sup 0/C has been determined by studying the microstructural changes in single crystals using transmission and analytical electron microscopy. The first detectable metallic phase, heterogeneously nucleated along dislocations within (100) and (001) subboundaries, had a composition Ni/sub 65/Fe/sub 35/ equilibrated with a CO/CO/sub 2/ gas mixture having an oxygen fugacity f/sub 02/ of 10/sup -5.6/ Pa. Although the (100) subboundaries contained a high density of dislocations with Burgers vector (100), the nucleation sites were restricted to (010) and (001) dislocations: a result consistent with the theory of heterogeneous nucleation along dislocations. Under the reducing conditions of an f2 of 10/sup -12/ Pa, a forsteritic olivine is produced at the gas-mineral interface with a high density of metallic precipitates (Fe/sub 96/Ni/sub 4/) homogeneously nucleated in the olivine. Nonstoichiometry of the olivine was inferred from the absence of any additional silica-rich phases. The nonstoichiometry was analyzed in terms of possible crystalline defect structures, especially vacancies, assuming no evaporative losses from the surface except an oxygen exchange reaction. On the basis of the model proposed, the highly reduced olivine would contain an excess of SiO/sub 2/ (x2 = 0.355 compared with a stoichiometric value of 0.333) from the surface to a depth of several micrometers.

  17. 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.

  18. Shock-Induced Transformation Exsolution Lamellae in Olivine in Black Veins of the Mbale Meteorite

    NASA Astrophysics Data System (ADS)

    Chen, M.; Wopenka, B.; El Goresy, A.

    1995-09-01

    Mbale is a shocked L6 chondrite [1]. Some shock-induced veins of 0.1 to 2 mm width intersect the meteorite. The veins consist of diaplectic plagioclase glass, unmelted silicate fragments including olivines and pyroxenes, and the shock-induced melt materials consisting of metal-troilite intergrowths, microcrystalline pyroxene and olivine, and silicate glass. Here we report the first finding of shock-induced exsolutions in olivine that appear as compositionally different lamellae which presumably formed at high pressure by inversion of olivine (alpha) to the beta+gamma polymorphs. Olivine compositions in the chondritic part of Mbale range from Fa(sub)22.5 to Fa(sub)26 (average Fa(sub)24). In contrast, the exsolved olivines in the shock-induced veins (30 to 100 mm in diameter) consist of alternating Fe-rich (Fa(sub)22-32) and Fe-poor (Fa(sub)9.9-18.5) lamellae that range in width from less than 0.5 micrometers to up to 10 micrometers. Each individual lamella actually consists of microcrystals of less than 0.5 micrometers in diameter with rather diffuse borders within the lamella. The lamellae occur in ~30 micrometer segments which were formed by faulting and displacement. Micro-Raman spectroscopy confirms that both types of exsolution lamellae currently have the olivine (alpha) structure. The partially melted veins of Mbale may have reached a post-shock peak temperature of 1473 K >= T <= 1873 K. Based on the phase diagrams of the olivine(alpha)-wadsleyite(beta)-ringwoodite(gamma) transformations in the system Mg(sub)2SiO(sub)4-Fe(sub)2SiO(sub)4 at 1473 K [2], olivine of composition ~Fa(sub)24 should exsolve at equilibrium conditionsins to beta- + gamma-phases at P >12.7 GPa, and transform to a single gamma-phase at >15 GPa. Figure 1 shows that the determined compositions of the Fe-rich and Fe-poor lamellae in Mbale match perfectly the compositions at the beta + gamma/gamma and the beta + gamma/beta phase boundaries, respectively. Since these grains depict well ordered lamellar structure displaced by several faults, the exsolution lamellae of olivine must have nucleated before faulting. TEM studies of ringwoodite in black veins in other shocked chondrites indicate that the original olivine has transformed into a mosaic of ringwoodite grains in nano-meter size range [3,4]. The observed lamellar structure in Mbale olivines is indicative of exsolution transformation from single grains before faulting of the olivines and definitely before solidification of the silicate melt to glass in the vein. We therefore consider it unlikely that the shock-induced olivine lamellae were produced via retrograde exsolution from gamma to gamma + beta. Our findings strongly suggest that the exsolutions were produced from an originally homogeneous olivine (alpha) by the following mechanism: Original homogenous olivine exsolved at P>12.7 GPa and 1473 K >=T <= 1873 K into Fe-poor beta- and Fe-rich gamma-phases possibly along [001] which is the predominant dislocation orientation in olivine during deformation [4,5]. The dislocations in olivine may have provided the nucleation sites for the beta- and gamma-phases due to their reduced activation barrier to nucleation. The grains were then faulted to several segments of 30 micrometers in diameter. A cooling rate of >= 260 K/s during the solidification of the shock-induced melt was estimated in the interval of 1223-1673 K, based on the metallic dendrite arm spacing or cell width of ~14 micrometers [6]. The cooling of the veins after the solidification of metal and silicate melts should have been much slower than 260 K/s because of the homogeneous Ni-concentration within the metallic dendrites. We interpret the survival of the lamellar structure as due to a nonlinear cooling rate: (1) very fast cooling after pressure release thus inhibiting obliteration of the lamellae by diffusion; followed by (2) slow cooling <1223 K thus leading to inversion of gamma and beta lamellae to alpha without chemical homogenization. References: [1] Jenniskens P. et al. (1994) Meteoritics , 29, 246-254. [2] Akaogi M. et al. (1989) JGR, 94, 15671-15685. [3] Madon M. and Poirier J. P. (1983) Phys. Earth Planet. Inter., 33, 31-44. [4] Price G. D. et al. (1979) Contrib. Mineral. Petrol., 71, 211-218. [5] Ashworth J. R. and Barber D. J. (1975) EPSL, 13, 43-50. [6] Scott E. R. D. (1982) GCA, 46, 813-823. Fig.1. Olivine (alpha)- wadsleyite (beta)- ringwoodite (gamma) relations in the system Mg(sub)2SiO(sub)4-Fe(sub)2SiO(sub)4 at 1473 K (after Akaogi et al. [2]). The compositions of the Fe-poor and Fe-rich lamellae of a representative olivine grain are plotted as open circles. Note that in all cases the compositions of the lamellae plot exactly at the the beta + gamma/beta and beta + gamma/gamma phase boundaries.

  19. Shock-induced fine-grained recrystallization of olivine - Evidence against subsolidus reduction of Fe/2+/

    NASA Technical Reports Server (NTRS)

    Ahrens, T. J.; Tsay, F.-D.; Live, D. H.

    1976-01-01

    Electron spin resonance (ESR) studies have been carried out on three single grains of terrestrial olivine (Fo90) shock loaded along the 010 line to peak pressures of 280, 330, and 440 kbar. The results indicate that neither metallic Fe similar to that observed in returned lunar soils nor paramagnetic Fe(3+) caused by oxidation of Fe(2+) has been produced in these shock experiments. Trace amounts of Mn (2+) have been detected in both shocked and unshocked olivine. The ESR signals of Mn(2+) show spectral features which are found to correlate with the degree of shock-induced recrystallization observed petrographically. The increasing mass fraction of recrystallized olivine correlates with increasing shock pressures. This phenomenon is modelled assuming it results from the progressive effect of the shock-induced transformation of the olivine to a yet unknown high-pressure phase and its subsequent reversion to the low-pressure olivine phase. The mass fraction of recrystallized material is predicted to be nearly linear with shock pressure.

  20. 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

  1. Near-infrared spectral reflectance of mineral mixtures - Systematic combinations of pyroxenes, olivine, and iron oxides

    NASA Technical Reports Server (NTRS)

    Singer, R. B.

    1981-01-01

    Near-infrared spectral reflectance data are presented for systematic variations in weight percent of two component mixtures of ferromagnesium and iron oxide minerals used to study the dark materials on Mars. Olivine spectral features are greatly reduced in contrast by admixture of other phases but remain distinctive even for low olivine contents. Clinopyroxene and orthopyroxene mixtures show resolved pyroxene absorptions near 2 microns. Limonite greatly modifies pyroxene and olivine reflectance, but does not fully eliminate distinctive spectral characteristics. Using only spectral data in the 1 micron region, it is difficult to differentiate orthopyroxene and limonite in a mixture. All composite mineral absorptions were either weaker than or intermediate in strength to the end-member absorptions and have bandwidths greater than or equal to those for the end members. In general, spectral properties in an intimate mixture combine in a complex, nonadditive manner, with features demonstrating a regular but usually nonlinear variation as a function of end-member phase proportions.

  2. 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 formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

  3. 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.

  4. 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.

  5. Peridotite and pyroxenite components in the sources of Grande Comore lavas: evidence from olivine compositions

    NASA Astrophysics Data System (ADS)

    Weiss, Y.; Class, C.; Goldstein, S. L.

    2013-12-01

    Grande Comore (Ngazidja) is the youngest Island of the Comores Archipelego in the Indian Ocean, located in the Somali Basin between Africa and Madagascar. The island formed by two volcanoes. Karthala is an active shield volcano, and La Grille is composed mainly of monogenetic cinder cones. The island represents interaction between a mantle plume and oceanic lithosphere and previous studies suggested, based on the major, trace elements and Sr-Nd-Pb-Os isotopic relationships of the lavas, that the alkali basalts of Karthala reflect mainly plume derived melts, while the basanites of La Grille are the products of interaction of plume melts with the metasomatized oceanic lithosphere. Here we report the chemical composition of olivine phenocrysts of Karthala lavas (5 samples), old Karthala (1) and La Grille (3) that were previously analyzed for their major, trace elements and Sr, Nd, Pb, Os and He isotopic compositions. Olivine phenocrysts from Karthala lavas have higher Mn and Ca, lower Al and slightly lower Ni content compared to olivines from La Grille at similar Mg#. Olivines from ';Old Karthala'are close in composition to those from La Grille and the content of Cr is similar between all three groups. The average Mn/Fe and Ca/Fe ratios of olivines of the samples positive correlate with the Sr-Pb-Os isotope ratios of the corresponding whole rocks, and Karthala has higher values than La Grille. These ratios negatively correlate with Nd-He isotope ratios, as well as with the La/Gd, Gd/Yb and Nb/K of the host lavas. The average Ni/Mg and Al/Mg ratios of the olivines correlate with the isotopic and trace element ratios of the whole rocks as well, but display trends in the opposite direction to the ones observed for Mn/Ca over Fe. Previous studies have proposed that the minor element (Ni, Mn and Ca) composition in olivine can be used to infer the proportions of peridotite vs pyroxenite and thus, the amount of recycled ocean crust in the source lithologies of magmas (Sobolev et al., 2007. The amount of recycled crust in sources of mantle-derived melts. Science, 306, 412-417). The Karthala olivines have high Mn/Fe and Ca/Fe and are similar in composition to olivines in MORB, suggesting 10-35% melt contribution from a pyroxenite source. La Grille and old Karthala olivines, on the other hand, are closer in composition to olivines from the Makapuu stage of the Koolau Island in Hawaii and represent 50-75% pyroxenite-derived melt. However, the Ni/Mg ratios in the Grande Comore lavas are relatively constant, unlike MORB, Koolau and other OIBs. Indeed the pyroxenite, which melts within the lithosphere to contribute to the La Grille and old Karthala lavas, most probably, due to metasomatic processes, differs from asthenospheric pyroxenite, which has been suggested to form by the interaction of recycled oceanic crust and peridotite in a rising plume. Thus, our data indicate that lithospheric pyroxenite formed by metasomatism of the lithospheric mantle can be distinguished from pyroxenite from mantle recycling from olivine phenocryst compositions in OIBs.

  6. 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.

  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. 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

  9. Laboratory spectra of amorphous and crystalline olivine: An application to comet Halley IR spectrum

    SciTech Connect

    Blanco, A.; Orofino, V. . Ist. di Fisica); Bussoletti, E.; Fonti, S. ); Colangeli, L. . Facolta' di Ingegneria); Stephens, J.R. )

    1990-01-01

    Among the various silicates proposed as components of cosmic dust grains, olivine is considered one of the most likely materials. In this work we present the infrared spectra of three different types of olivine grains: crystalline, amorphous, and synthetic (also amorphous). While the first and second sample derive from the same natural mineral, the third one has been prepared in laboratory according to the relative cosmic abundances of the elements. The experiment data are used to fit the emission feature observed in the comet Halley spectrum between 8 and 13 {mu}m. Satisfactory results are obtained by using synthetic olivine mixed with a small amount (5%) of crystalline grains. 4 refs., 2 figs.

  10. 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

  11. Rheological contrast between olivine and garnet at high pressures under anhydrous conditions

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    In this study, we carried out experiments investigating the rheological contrast between olivine and garnet, two major components of the mantle, at mantle temperatures and pressures. Experiments were carried out using a deformation-DIA at the National Synchrotron Light Source at Brookhaven National Laboratory. Samples were fabricated from powdered minerals; olivine was from San Carlos and garnet from the Dabie-Sulu orogenic belt in China. In the experiments, a cold-pressed cylinder of fine-grained olivine and one of garnet, each with a diameter of ~1.1 mm and a length of ~0.8 mm, were stacked together, separated by a nickel foil disk. This duplex sample was assembled with alumina pistons, a boron nitride sleeve, and graphite resistance heater into a 6.2-mm edge length cubic mullite-pyrophyllite pressure cell. Experiments were carried out at 1373 - 1573 K and pressures of 3 - 5 GPa. With the synchrotron x-ray beam, a time series of in-situ radiographs enables monitoring of the instantaneous lengths of both deforming samples at the same temperature, pressure, and load. At our experimental conditions, both samples deform with stress exponents of n ≈ 3 and with activation energies of Q ≈ 300 kJ/mol. Samples of olivine deform only a factor of ~1.5 faster than samples of garnet of similar grain size, indicating that there is no significant rheological contrast between samples of olivine and garnet under anhydrous conditions. This result, which is the first direct comparison of the rheological behavior of olivine and garnet, provides a solid basis for modeling the rheological structures of subducted lithosphere.

  12. 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.

  13. 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.

  14. 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

  15. 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 sulfur-rich volcanism, and sulfur-rich surface deposits also makes it very likely that sulfate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above -40degC on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfaterich material have been detected on and around the modern north polar region of Mars. The prevalence of ice-dust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself.

  16. 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, which prevents strong olivine CPO patterns from forming. We show B-type Ol CPO can form as a result of static topotactic growth of olivine after high-temperature breakdown of foliated serpentinite. These results resolve the discrepancies between experimental and natural examples of B-type CPO and show the need to rethink the formation process of olivine CPO in convergent margins. Topotactic growth of olivine after antigorite can account for the inferred distribution of B-type Ol CPO in the mantle wedge more successfully than dislocation creep.

  17. Olivine Composition of the Mars Trojan 5261 Eureka: Spitzer IRS Data

    NASA Technical Reports Server (NTRS)

    Lim, L. F.; Burt, B. J.; Emery, J. P.; Mueller, M.; Rivkin, A. S.; Trilling, D.

    2011-01-01

    The largest Mars trojan, 5261 Eureka, is one of two prototype "Sa" asteroids in the Bus-Demeo taxonomy. Analysis of its visible/near-IR spectrum led to the conclusion that it might represent either an angritic analog or an olivine-rich composition such as an R chondrite. Spitzer IRS data (5-30 micrometers) have enabled us to resolve this ambiguity. The thermal-IR spectrum exhibits strong olivine reststrahlen features consistent with a composition of approximately equals Fo60-70. Laboratory spectra of R chondrites, brachinites, and chassignites are dominated by similar features.

  18. 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.

  19. Seismic evidence for olivine phase changes at the 410- and 660-kilometer discontinuities.

    PubMed

    Lebedev, Sergei; Chevrot, Sbastien; 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

  20. 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+/?Fe) 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+/?Fe in olivine-hosted melt inclusions, permitting the recovery of the true extent of magmatic redox variability present at the time of inclusion trapping.

  1. 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

  2. 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.

  3. 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 recrystallisation on the boundaries of parent grains. At 1100C, the degree of recrystallization increased with deformation becoming increasingly concentrated on grain boundaries near parallel to the orientation of the strain marker. In all experiments we have performed so far, the stress continuously increased with strain, and no evidence of weakening nor shear localization was observed. However, the degree of recrystallization systematically increased with temperature, and evidence for mixing of recrystallised orthopyroxene and olivine grains was observed. At higher temperature, higher water content and/or lower strain-rates, the influence of dynamic recrystallization will be more extensive.

  4. 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 in immature and submature lunar soils and indicate surface exposures of approx. 10(exp 5) years. The outermost few nanometers of the disordered rims on Hayabusa olivines are more Si-rich and Mg- and Fe-depleted relative to the cores of the grains and likely represent a minor accumulation of impact-generated vapors or sputter deposits. Nanophase Fe metal particles are less abundant in the Hayabusa rims compared to the rims on lunar grains. Conclusions: The Hayabusa and lunar olivine grain rims have widths and microstructures consistent with formation from atomic displacement damage from solar wind ions. The space weathering features in the Hayabusa grains are similar to those observed in olivines from immature to submature lunar soils. A major difference, however, is that the Hayabusa grains appear to lack the hypervelocity impact products (melt spherules, thick vapor deposits, and abundant nanophase Fe metal particles) that are common in lunar soil grains with a similar exposure history.

  5. Nitrogen Isotopes in Olivine Separates from Volcanic Arcs, Hot Spots and Continental Mantle Xenoliths

    NASA Astrophysics Data System (ADS)

    Fischer, T. P.; Takahata, N.; Sano, Y.; Hilton, D. R.

    2004-12-01

    We report the first nitrogen isotopic data of olivine separates from volcanic arcs (Cerro Negro, Nicaragua; Izalco, El Salvador; Turrialba, Costa Rica; Ichinomegata, Japan). In addition, we report nitrogen isotopic data of olivine separates from ocean islands (Hawaii, Reunion, Iceland) and continental mantle xenoliths (San Carlos, Arizona). Samples were processed by crushing and analyzed using a modified noble gas mass spectrometer (VG3400). N concentrations range from 0.6 to 22 micro ccSTP/g olivine. The 15N/14N ratios (expressed in the δ 15N notation where δ 15N sample = {[(15N/14N)sample/(15N/14N)Air]-1} X 1000) of olivine separates are distinctly different from air (0.0‰ ) and range from lower than mean MORB (- 5 ‰ ) to values characteristic of (subducted) oceanic sediments (+ 7 ‰ ). Positive δ 15N values are found in olivines from volcanic arcs: Cerro Negro 1992 ash (+ 6.2 ± 1.6‰ ), Izalco lava flow (+ 5.1 ± 0.7‰ ), Ichinomengata spinel lherzolite (+ 1.1 ± 0.5 ‰ ) with the exception of Turrialba lava (- 1.7 ± 2.5‰ ). Olivines from hot spots have both positive and negative δ 15N signatures: Iceland, Theistareykir - northern rift zone (- 8± 1.6 ‰ ), Hawaii, dunite from 1801 Kaupulehu flow of Hualuai volcano (+ 3.1 ± 0.3 ‰ ) and Reunion dunite (+ 0.2 ± 0.5‰ ). The San Carlos mantle xenolith has a value of - 1.5 ± 2.5‰ . 40Ar/36Ar ratios of the samples as determined in this study or reported in the literature are significantly higher than air (295.5) in olivines from Ichinomegata, San Carlos, Iceland, Reunion and Hawaii. The olivines from Cerro Negro have a 40Ar/36Ar ratio of 306, close to that of air. The 3He/4He ratios of the samples are higher than the MORB value of 8.0 RA (RA is the 3He/4He of air), the exception being Cerro Negro (6.1 RA). Hawaii, Reunion and Iceland have 3He/4He of 10.3, 12.9 and 12.3 RA, respectively. δ 15N signatures of fumarole gas samples collected at Cerro Negro (+ 4.9 ±0.1 ‰ ), Turrialba (- 1.0 ±0.3 ‰ ) and localities close to Izalco (+ 4.0 ±0.4‰ ) are identical (within error) to those of the olivine separates. The results obtained in this study are significant and show that 1) N isotopes in olivine separates and volcanic/hydrothermal gas emissions both sample volatiles that are primarily derived from the magma source. 2) subduction of oceanic sediments and transfer of N through the mantle wedge controls the N isotopic composition in volcanic arcs as sampled by olivine separates and gas discharges. 3) the N isotopic signature of hot spot related volatiles is variable but the samples from Hawaii, and to a lesser extent from Reunion, support the idea that surficial N (from subducted sediments or oceanic basement) is recycled into the lower mantle. 4) N as sampled by the San Carlos mantle xenolith may record a greater extent of air contamination than the other samples. Alternatively, N data of San Carlos and the Iceland northern rift zone suggests that the N isotopic signature of the upper mantle may be more variable than previously inferred from MORB samples.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Correlative Microscopy and Visible/Near-Infrared Spectral Analysis of Simulated Solar Wind Implanted Olivine

    NASA Astrophysics Data System (ADS)

    Kuhlman, K. R.; Kvit, A. V.; Baba, K.; Poplawsky, J. D.; Hiroi, T.; Isheim, D.

    2015-11-01

    Here we present the results of the first atom probe tomography (APT) and scanning transmission electron microscopy study (STEM) of San Carlos olivine (Fo90.1) exposed to simulated solar wind-based space weathering due to hydrogen (~1keV/amu).

  11. Pyroxenes and olivines: Structural implications of shock-wave data for high pressure phases

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.; Ahrens, T. J.

    1975-01-01

    The nature of the shock-induced, high-pressure phases of olivine and pyroxene rocks is examined in the light of data for the densities of a new class of perovskite-related silicate structures. Also examined are some new Hugoniot and release adiabat data for bronzite. Reexamining available shock data for magnesian pyroxenes and olivines leads to the conclusion that they define a mixed phase (or disequilibrium) region to about the 100 GPa range, related to the kinetics of phase transformation in these silicates. By recognizing this point, certain discrepancies in previous interpretations of shock data can be explained. A set of theoretical Hugonoits for pyroxene and olivine stoichiometry, perovskite-bearing assemblages was constructed based on their properties deduced from high-pressure work, showing that the shock data is compatible with transformations to perovskites in the 45-7GPa region. Finally, the shock data indicate very similar properties for olivine and pyroxene at high pressures making them both equally likely candidates for the lower mantle.

  12. 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.

  13. The fate of fluid inclusions during high-temperature experimental deformation of olivine aggregates

    NASA Astrophysics Data System (ADS)

    Carter, Matthew J.; Zimmerman, Mark E.; Teyssier, Christian

    2015-05-01

    Torsion experiments on initially wet and dry olivine aggregates at equivalent deformation conditions investigated the fate of fluid inclusions (FIs) during high-temperature deformation. Wet samples were produced by adding water to San Carlos olivine powders before hot pressing; those hot pressed without water are considered dry. After hot pressing, wet and dry aggregates have comparable grain sizes, but wet aggregates have more abundant primary FIs. Talc jackets were fitted around some wet and dry samples prior to deformation to hydrate samples during deformation via talc dehydration at elevated temperature, whereas other samples were deformed without talc. At similar strain rates (~1.0 × 10-4 s-1), the peak shear stress for the dry sample (no talc) was 190-220 MPa, whereas all other samples reached 180 MPa; the strengths of wet (± talc) and dry (+ talc) specimens appear similar. Deformed samples reveal abundant FIs, reduced grain size, shape preferred orientation of olivine, and a pervasive low-angle fabric (C') to the shear plane defined by aligned FIs. Samples deformed with talc have FI-rich and FI-depleted domains; where FIs are abundant, the C' fabric is better developed and grain size is smaller. Electron backscatter diffraction pole figures suggest that olivine deformed in the dislocation creep regime via the (010)[100] slip system. Results of these experiments suggest that FIs are redistributed during dislocation creep, leading to the development of grain-scale, high-diffusivity pathways.

  14. 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.

  15. 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.

  16. 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.

  17. 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 al., 1982). This is apparently due to greater dislocation densities for Fe-rich olivines, and oxidation of Fe^2+. If a similar phenomenon affects alteration of pyroxenes and olivines to smectite, then the genetic relation of hydrous to anhydrous IDPs is permitted by our results. We have already reported that the Mg-Fe compositional range exhibited by phyllosilicates in hydrated IDPs is nearly identical to that of olivines and pyroxenes in anhydrous IDPs (Zolensky and Lindstrom, 1992); this observation also permits a genetic link between these IDP types. However, it is also possible that hydrous are not genetically related to anhydrous IDPs. We note that the relatively Mg-rich compositions of olivines and orthopyroxenes in sulfate-containing IDPs can also be explained by preferential destruction of Fe-rich olivines by oxidation of Fe^2+. The ablated IDPs are merely showing the results of equilibration. Are chondritic IDPs merely small samples of the parent bodies of chondritic meteorites? Aside from differences in bulk composition and physical properties, IDPs differ from all chondritic meteorites except CIs and CMs in the compositional ranges of olivines and pyroxenes (for olivines: CV3- Fo40-60; CO3- Fo40-70; H3, L3 and LL3- Fo30-80; Scott et al., 1988; Dodd, 1981). Although a few hydrous IDPs (a subset of the serpentine class particles) are apparently related to CMs (Zolensky and Lindstrom, 1992), the majority are mineralogically dissimilar. Small carbonaceous clasts contained within certain meteorites (e.g., CR chondrites, the Bholghati howardite, LEW 85300 polymict eucrite and Kaidun carbonaceous breccia) have similar mineralogies to some IDPs (Zolensky et al., 1992), although more detailed analyses of these materials are still required. In summary, most chondritic IDPs are compositionally and mineralogically distinct from chondritic meteorites, but have apparently experienced similar conditions of origin and evolution both in the solar nebula and on parent bodies. References: Bradley and Brownlee (1991) Science 251, 549; Deer, Howie, and Zussman (1982) Rock-Forming Minerals, p. 77; Dodd (1981) Meteorites, A Petrologic-Chemical Synthesis, p. 45; Scott et al. (1988) in Meteorites and the Early Solar System, 721; Zolensky and Lindstrom (1992) Proc. Lunar and Planet. Sci. Conf. 22, 161; Zolensky et al. (1992) Lunar and Planet. Sci. XXIV, 1587.

  18. Methodology of Space Weathering Simulation and Its Application on Olivine and Pyroxene Samples

    NASA Astrophysics Data System (ADS)

    Malina, Ondrej; Kohout, Tomas; Tucek, Jiri; Filip, Jan; Britt, Daniel; Zboril, Radek

    2015-11-01

    Here, we reported a two-step thermal treatment method [1] for the space weathering simulation and the differences in the formation of metallic iron nanoparticles (npFe0) on the surface of olivine and pyroxene samples are discussed.In general, the main goal is in controlled size of npFe0 formed on the surface of olivine and pyroxene and in quantification of the related spectral changes. The transmission electron microscopy (TEM) after double-heating method revealed two significant features. First, different sizes and concentration of npFe0 are observed, and secondly, due to more resistance of pyroxene (e.g. [2]), higher temperatures are needed to produce the same amount of npFe0 as in the olivine case. [1]Results from TEM are fully consistent with reflectance spectra, which show progressive changes as a function of the increasing npFe0 amount. The reason for the observed differences in reflectance spectra can be found in the crystal structure and local environment at each crystallographic position of both samples. It is very similar as in the case of laser heating experiments (e.g. [2]), where the surface of orthopyroxene is significantly more resistant to reduction than olivine due to mobility of oxygen and cation diffusions from the bulk to surface of the samples.References:[1] Kohout T. et al. (2014) Icarus, 237, 75-83[2] Quadery A. et al (2015) JGR-Planets 120, 1-19.

  19. 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. Mineral Compositions from the Hawaii Scientific Drilling Project (HSDP): Preliminary Results Part III - Olivine

    NASA Astrophysics Data System (ADS)

    Putirka, K. D.; Smart, C. M.; Polfer, K. M.

    2004-12-01

    Olivines are the most prevalent phenocrysts in Hawaiian lavas and thus offer a more complete temporal coverage of magmatic processes compared to phenocrysts of more restricted occurrence. As in parts I and II (see accompanying abstracts) we examine olivine compositions from HSDP core samples, which provide a temporal view of the Mauna Kea magma plumbing system. In general, mineral compositions are valuable because they provide an archive of liquid compositions; the compositional record of liquids is always murky due to the facility with which liquids are blended. But minerals, such as olivine, are resistant to re-equilibration and hence provide a much more complete record of the range of liquid compositions that enter a magma plumbing system. Olivine compositions are of particular interest since the Fo content (Mg/(Mg + Fe) ratio) is highly sensitive to T. Olivines that are sampled through the HSDP core thus provide a window into temperature variations across the Hawaiian hot spot. Most olivines are not in Fe-Mg exchange equilibrium with their host whole rock samples. This results is unsurprising and has been noted in numerous studies of olivine phenocrysts at Hawaii. This lack of equilibration limits the precision with which crystallization temperatures can be extracted. But comparisons of Mg/(Mg + Fe) (Fo content) with core depth reveal interesting qualitative results. Most notable are two aspects: (a) Fo contents exhibit nearly constant maximum values throughout the 3000 m of core, near Fo = 90. (b) In contrast, minimum Fo values appear to decrease with decreasing depth. The first observation is counter to what was expected. As Mauna Kea moved over the hot spot, one might expect maximum temperatures to decrease in response to the tapping of cooler mantle material. But near constant maximum values suggest that the hottest parts of the plume are delivered to Hawaiian conduits throughout their eruptive history. In contrast, the decrease in minimum Fo values with time might indeed reflect some T variation across the plume, and is consistent with observations of plagioclase (see part II). We hypothesize that the progressive decrease of Fo contents reflects a gradual decline in eruptive recurrence intervals: as magma supply rates wane, and eruption recurrence intervals increase, the magma conduit may progressively become choked off at various depths, with the result that individual magma batches are stored at a greater range of depths for longer periods of time. But even as supply rates decline, the hottest magmas that are supplied to a conduit during the shield-building stage seem somehow to still be available to the conduit during waning periods of volcanic activity.

  1. Elasticity of single-crystal olivine at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Mao, Zhu; Fan, Dawei; Lin, Jung-Fu; Yang, Jing; Tkachev, Sergey N.; Zhuravlev, Kirill; Prakapenka, Vitali B.

    2015-09-01

    Elasticity of single-crystal San Carlos olivine has been derived from sound velocity and density measurements at simultaneous high pressure-temperature conditions up to 20 GPa and 900 K using in situ Brillouin spectroscopy and single-crystal X-ray diffraction in externally-heated diamond anvil cells. These experimental results are used to evaluate the combined effect of pressure and temperature on full elastic constants of single-crystal olivine to better understand its velocity profiles and anisotropies in the deep mantle. Analysis of the results shows that the shear moduli display strong concave behaviors as a function of pressure at a given high temperature, while the longitudinal modulus, C11, and the off-diagonal moduli, C12 and C13, exhibit greater temperature dependence at higher pressures than at relatively lower pressures. Using a finite-strain theory and thermal equation of state modeling for a pyrolitic mantle composition along an expected mantle geotherm, our results show that the magnitude of the VP and VS jumps at the 410-km depth are 6% and 6.4%, respectively, which are greater than that found in seismic observations, suggesting a mantle olivine content of 40-50 vol%, which is less than what is expected for the pyrolite model. Our modeled velocity profiles for a metastable olivine wedge in the subduction slabs along a representative cold slab geotherm are 6% and 10% lower than those of wadsleyite and ringwoodite, respectively, at corresponding depths of the normal mantle. Our modeled results also show that metastable olivine in the cold slabs could have strong VP and VS anisotropies. The maximum VP anisotropy is estimated to be 19-22% at transition zone depth, whereas the maximum VS splitting is 13-23% and increases with depth. As a result, the presence of a metastable olivine wedge at the transition zone depth would exhibit a seismic signature of low velocity and strong seismic anisotropy which are consistent with recent seismic observations for various locations of the slabs and can be used as mineral physics constraints for future seismic detections of the metastable olivine wedges in the deep mantle.

  2. Origin of Aristarchus Olivine Deposits Based on M3, WAC, and Diviner Analyses

    NASA Astrophysics Data System (ADS)

    Wiseman, S. M.; Mustard, J. F.; Donaldson Hanna, K. L.; Isaacson, P.; Jolliff, B. L.; Besse, S.; Staid, M.; Pieters, C. M.

    2011-12-01

    The Aristarchus region contains geologically diverse deposits and the Aristarchus impact crater, located on the SE margin of the plateau near the contact between plateau materials and western Procellarum basalts, has exposed materials with variable compositions. Of particular interest is the origin of olivine-bearing deposits that occur on the SE portion of the crater rim and ejecta in association with impact melt [1]. NW portions of the rim and ejecta expose plateau materials and are spectrally dominated by pyroxene in the VNIR. Spectra of the NW rim and ejecta are consistent with a noritic composition and with the inferred origin of the plateau as uplifted upper crust [2,3,4]. Therefore, it is unlikely that the olivine- bearing materials, which exhibit a strong 1 micron olivine absorption and only minor pyroxene contributions, are derived from plateau materials similar to those exposed in the NW portion of the crater. Potential sources of the olivine-bearing material excavated by the impact include western Procellarum basalts or buried material associated with the Marius Hills volcanic complex. Alternatively, the olivine-bearing deposits could be derived from a shallow pluton that is not represented by other surface exposures or could have formed as re-crystallized impact melt. Both the western Procellarum basalts [5,6] and some units associated with the Marius Hills [7] are olivine-bearing. In order to differentiate between these hypotheses, we are integrating spectral data in the UV/VIS (LRO WAC), VIS/NIR (Chandrayaan-1 M3), and TIR (LRO Diviner) to further characterize the assemblages of minerals that occur in association with the olivine-bearing deposits in Aristarchus crater, western Procellarum, and units within the Marius Hills volcanic complex. [1] Mustard et al., 2011, JGR 116. [2] McEwen et al., 1994, Science 266. [3] Lucey et al., 1986, LPSC 16. [4] Chevrel et al., 2009, Icarus 199. [5] Staid and Pieters 2001, JGR. [6] Staid et al., 2011, JGR 116. [7] Besse et al., 2011, JGR 116.

  3. 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 aqueous alteration of olivine in carbonate and silica-rich solutions. H2 was formed linearly at 70 °C, probably coupled to Fe(II) oxidation. Gas, liquid and solid phases were studied and coupled to geochemical modeling. Amorphous and microcrystalline talc-like precipitations were formed. Zn concentration in solution is increasing linearly with time and temperature.

  4. UNDERSTANDING OLIVINE CO2 MINERAL SEQUESTRATION MECHANISMS AT THE ATOMIC LEVEL: OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    M.J. McKelvy; H. Bearat; A.V.G. Chizmeshya; R. Nunez; R.W. Carpenter

    2003-08-01

    Carbonation of Mg-rich minerals offers an intriguing candidate carbon sequestration process technology, which can provide large-scale CO{sub 2} disposal. Such disposal bypasses many long-term storage problems by (i) providing containment in the form of mineral carbonates that have proven stable over geological time, (ii) generating only environmentally benign materials, and (iii) essentially eliminating the need for continuous site monitoring. The primary challenge for viable process development is reducing process cost. This is the primary focus of the CO{sub 2} Mineral Sequestration Working Group managed by Fossil Energy at DOE, which includes members from the Albany Research Center, Los Alamos National Laboratory, the National Energy Technology Laboratory, Penn State University, Science Applications International Corporation, and the University of Utah, as well as from our research group at Arizona State University. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a leading process candidate, which converts CO{sub 2} into the mineral magnesite (MgCO{sub 3}). As olivine carbonation is exothermic, it offers intriguing low-cost potential. Recent studies at the Albany Research Center have found aqueous-solution carbonation is a promising approach. Cost effectively enhancing carbonation reactivity is central to reducing process cost. Many of the mechanisms that impact reactivity occur at the solid/solution interface. Understanding these mechanisms is central to the ability to engineer new and modified processes to enhance carbonation reactivity and lower cost. Herein, we report the results of our UCR I project, which focused on exploring the reaction mechanisms that govern aqueous-solution olivine carbonation using model olivine feedstock materials. Carbonation was found to be a complex process associated with passivating silica layer formation, which includes the trapping of magnesite nanocrystals within the passivating silica layers, cracking and exfoliation of the layers, silica surface migration, olivine etch pit formation, transfer of the Mg and Fe in the olivine into the product carbonate, and the nucleation and growth of magnesite crystals on/in the silica/olivine reaction matrix. These phenomena occur in concert with the large solid volume changes that accompany the carbonation process, which can substantially impact carbonation reactivity. Passivating silica layer formation appears to play a major role in inhibiting carbonation reactivity. New approaches that can mitigate the effectiveness of passivating layer formation may offer intriguing potential to enhance carbonation reactivity and lower process cost.

  5. Fault Reactivation During the Olivine to Wadsleyite Transition: A Mechanism for Deep Focus Earthquakes

    NASA Astrophysics Data System (ADS)

    Dobson, D.; de Ronde, A.; Heidelbach, F.; Meredith, P.; Boon, S.

    2006-12-01

    Slip plane orientations of some deep-focus earthquakes suggest that earthquakes can be triggered by reactivation of pre-existing faults in the transition zone. In order to test this theory, we have studied the effect of the olivine-wadsleyite transition on the remobilization of pre-existing olivine faults by performing axisymmetric deformation experiments in a multi-anvil apparatus. Experiments were performed on 3 mm long, 1.5 mm wide cores of San Carlos olivine polycrystals at temperatures of 1173-1273 K and pressures of 6-14 GPa. Microseismicity (AE) related to brittle events in the sample was monitored using 8 1-5 MHz bandwidth PZT transducers that are attached to the back truncations of the tungsten carbide anvils. Cold axisymmetric compression of olivine to 6 GPa pressure results in a conical fault system that crosscuts the sample. AE hypocenters locate near faults and indicate high P-low T frictional sliding. The fault zones consist of fine-grained olivine gouge with a fractal dimension of 2.6±0.1 between 0.1-10 μm grain sizes. The gouge has a random CPO after isothermal compression from 6 to 7 GPa at 1173 K in 1 hour. AE signals from the fault zones during hot compression were indistinguishable from those observed during cold compression and near consistent with stick-slip behavior. Subsequent isothermal compression into the wadsleyite stability field shows no AE-activity. A pre-existing olivine fault zone deformed at 14 GPa and 1173-1273 K was replaced in 20 minutes by wadsleyite with a narrow grain size range (~0.8-1.0 μm). Fault zone wadsleyite has a clear CPO with a- and b-axes oriented in the direction of and perpendicular to the shear direction respectively. This suggests that wadsleyite accommodated renewed fault displacement by dislocation creep. Wadsleyite outside the fault zones does not have a CPO. Thus, under these conditions, fault zone wadsleyite appears weaker than the "wall rock" olivine, suggesting a mechanical weakening during the transition. Such a shear localization process on old faults might contribute to seismogenic slip within the Earth, where run-away processes are possible.

  6. High Melt Porosity in the Lower Oceanic Crust Inferred from Phosphorus Zoning in Olivine

    NASA Astrophysics Data System (ADS)

    Hellebrand, E.; Welsch, B. T.; Hammer, J. E.

    2013-12-01

    The canonical view that the lower oceanic crust is composed of cumulates of fractional crystallization has been intensely debated in recent years. Migrating melts, reacting with previously crystallized minerals in the crystal mush, can modify the mineralogy and phase proportions inside the lower crust, as well as the composition of erupted MORB [1]. An extreme product of reactive melt migration was discovered during IODP Legs 304/305 at Atlantis Massif (MAR 30N). In this 1.5 km deep drillhole, there are several sequences of olivine-rich troctolite with ';textbook cumulate texture', which may be associated with the contact of a gabbroic pluton into peridotite [2,3]. While there is little ambiguity about the geological relationships, the exact mechanism for the in-situ reactive transformation of mantle peridotites into lower crustal gabbroic lithologies is still poorly understood. One widespread textural feature in support of the dominant role of reactive melt migration is the occurrence of interstitial and vermicular high-Mg# cpx, which form post-compaction at very low melt porosities. The rare screens of opx-bearing mantle peridotites in this drillhole also preserve evidence for low-porosity replacement of mantle opx by gabbroic cpx [4], with minimal volume change. However, we will show that a significant and possibly the main mass of the olivine crystals in the olivine-rich troctolites do not form at low melt porosities, but instead in a melt-rich local environment. Initially, olivines crystallize as rapidly grown dendrites, which is marked by distinct enrichments of the slowly diffusing element phosphorus. Subsequent slow growth produces the main mass of the otherwise P-free olivine crystal. Our observations on natural basalt-hosted and experimentally grown olivines indicate that strong undercooling in a crystal-poor environment is required for dendrite formation. By extrapolation, this would require a crystal-poor melt lens at the top of an evolving gabbroic intrusion into overlying lithospheric mantle peridotites. Disintegration and partial dissolution of the peridotite minerals can provide the conditions for compositional (rather than thermal) undercooling and promote the rapid growth of new olivines inside the deep melt lens. [1] Lissenberg, C.J. & Dick, H.J.B. (2008) EPSL 271, 311-325. [2] Suhr, G. et al. (2008) G3, doi: 10.1029/2008GC002012. [3] Drouin, M. et al. (2009) Chem. Geol. 264, 71-88. [4] von der Handt, A. & Hellebrand, E. (2010) AGU Fall Meeting abstract.

  7. Deformation mechanism maps of olivine and rheology of the continental upper mantle

    NASA Astrophysics Data System (ADS)

    Wang, Q.

    2009-12-01

    The reliability of straightforward extrapolation of the laboratory-determined constitutive equations to the upper mantle depends on good quality of experimental data as well as the activation of same deformation mechanism at the much lower natural strain rates and stress. Recent laboratory studies have provided more accurate flow law parameters for olivine under both dry and wet conditions, which allow us to investigate deformation mechanisms of olivine and the mantle rheology more confidently. To compare rheology of the continental upper mantle in different geological settings, the western Superior Province (Canada), the Dabie Mountains and the North Jiangsu basin (China) are selected to represent an Archean craton, a Triassic continental collision zone and a Cenozoic intracratonic rift basin, respectively. Deformation mechanism maps of olivine were constructed under P-T conditions of the three tectonic units, and in a continental subduction zone characterized by P=6.28 GPa and T=900 °C. For dry olivine, diffusion creep is the dominant mechanism in all the cases, which is contrary to the widely observed lattice-preferred orientation of olivine in peridotite xenoliths and tectonites. For wet olivine, a small amount of water (50 H/106Si) can remarkably decrease the stress of dislocation creep and increase contribution of dislocation creep to the deformation of olivine in the upper mantle. In contrast, the effect of water to diffusion creep is ignorable when water content is less than 100 H/106Si. Combined with a compilation of water contents of natural olivine, rheology of the continental upper mantle is controlled by power law creep of wet olivine, and diffusion creep is the dominant deformation mechanism in the asthenosphere, especially for fine-grained peridotites. The Lehmann discontinuity characterized by the rapid decrease in seismic anisotropy at depth of ~220 km can be attributed to the transition from dislocation creep to diffusion creep in most regions, or to the pressure-induced olivine fabric transition from [100] slip to [001] slip in cold subduction zones. The effective viscosity (η) profiles indicate remarkable rheological contrast among the three units at depth <120 km and a decreasing viscosity difference with depth. At depth >250 km, the values of effective viscosity are very similar in different units, implying that changes in water contents and composition will control rheological contrast of the deep upper mantle. The mechanical lithosphere-asthenosphere boundary (LAB) can be defined as the depth where dη/dP changes from the negative to positive (e.g., a sharp LAB beneath the Dabie Mountains and the North Jiangsu basin) or the absolute value of dη/dP is less than 5×1012 s (e.g., a diffuse LAB beneath the western Superior Province). The LAB is about 250 km, 140 km and 75 km beneath the western Superior Province, the Dabie Mountains and the North Jiangsu basin, respectively. The sharp LAB (5-10 km thick) favors the lithosphere-asthenosphere decoupling beneath orogenic belts and rifts, while the diffuse LAB (~30 km thick) will lead to coherent deformation of the upper mantle and protect the continental roots from convective erosion. Hence the small pressure derivative of viscosity caused by cold and thick thermal lithosphere is the key to preserve continental roots.

  8. Mechanisms and Timescales for Reequilibration of Water in Olivine-Hosted Melt Inclusions

    NASA Astrophysics Data System (ADS)

    Gaetani, G. A.; O'Leary, J. A.; Shimizu, N.

    2009-12-01

    Water solubility in silicate melts drops substantially with decreasing pressure. A magma containing several weight % dissolved H2O in the shallow crust is left with only a few thousand ppm following eruption. Olivine-hosted melt inclusions provide information on the pre-eruptive H2O contents of degassed magmas because the strength of the host crystal protects the melt inclusion from the decompression experienced by the entraining magma. The principal uncertainty involved with interpreting pre-eruptive H2O concentrations from melt inclusions is the potential for diffusive loss or gain of H+ (protons) through the host olivine. It has been proposed that Fe redox reactions severely limit the proton flux, and that episodes of H2O loss/gain are easily identifiable through changes in oxidation state of the inclusion [1,2]. Results from hydration and dehydration experiments carried out on natural inclusion-bearing olivines and analyzed by SIMS confirm that H2O re-equilibratrion occurs rapidly via proton diffusion through the host olivine, and demonstrate that re-equilibration of oxygen fugacity within the inclusions occurs on comparable timescales via diffusion of point defects. Therefore, an olivine-hosted melt inclusion only provides a reliable record for the H2O content of the external melt with which it most recently equilibrated. Hydration experiments were performed on olivines from Puu Wahi, a scoria cone on the NE rift zone of Mauna Loa volcano. Melt inclusions initially containing 0.36±0.05 wt% H2O were held at 1 GPa and 1250°C in water enriched in 18O (18O/ΣO = 0.977) and D (2H/ΣH = 0.998) to map the transport of protons and oxygen during equilibration of melt inclusions with an external fluid. Dehydration experiments were carried out for 1 to 18 hrs at 1 bar and 1250 °C on inclusion-bearing olivines in scoria erupted from Cerro Negro volcano, Nicaragua, in 1999. The initial concentration of H2O in these melt inclusions is uniformly high (3.6±0.6 wt%). All run products were analyzed by SIMS on the Cameca 1280 ion microprobe at WHOI. Results from our experiments confirm that the mechanism for loss or gain of H2O from olivine-hosted melt inclusions is lattice diffusion of protons. This process leaves behind an O2- for every 2 protons lost, and scavenges an O2- for every 2 protons gained, producing an increase or decrease, respectively, of the fugacity of oxygen within the inclusion. However, H2O loss/gain for olivine-hosted melt inclusions is coupled with point defect-mediated oxygen fugacity re-equilibration. Therefore, Fe redox reactions do not limit either the amount or rate of water loss or gain by the inclusion. The H2O concentration of an olivine-hosted melt inclusion can change rapidly, and that change is not recorded by the oxygen fugacity of the melt. References: [1] A. V. Sobolev, L. V. Danyushevsky, J Petrol 35, 1183 (1994); [2] L. V. Danyushevsky, A. W. McNeill, A. V. Sobolev, Chem Geol 183, 5 (2002).

  9. Kinetics of the olivine-ringwoodite transformation and seismic attenuation in the Earth's mantle transition zone

    NASA Astrophysics Data System (ADS)

    Perrillat, J. P.; Chollet, M.; Durand, S.; van de Moortèle, B.; Chambat, F.; Mezouar, M.; Daniel, I.

    2016-01-01

    In regions of the mantle where multi-phases coexist like at the olivine-wadsleyite-ringwoodite transitions, the stress induced by the seismic waves may drive a mineralogical reaction between the low to high pressure phases, a possible source of dissipation. In such a situation, the amount of attenuation critically depends on the timescale for the phase transformations to reach equilibrium relative to the period of the seismic wave. Here we report synchrotron-based measurements of the kinetics of the olivine to ringwoodite transformation at pressure-temperature conditions of the co-stability loop, for iron-rich olivine compositions. Both microstructural and kinetic data suggest that the transformation rates are controlled by growth processes after the early saturation of nucleation sites along olivine grain boundaries. Transformation-time data show an increase of reaction rates with temperature and iron content, and have been fitted to a rate equation for interface-controlled transformation: G =k0 ṡ T ṡ exp ⁡ [ n ṡXFa ] ṡ exp ⁡ [ - (ΔHa + PV*) / RT ] × [ 1 - exp ⁡ (ΔGr / RT) ], where XFa is the fayalite fraction, the exponential factor n = 9.7, ln ⁡k0 = - 9.1 ms-1. XFa-1 and ΔHa = 199 kJ /mol, assuming V* = 0 cm3 /mol. Including these new kinetic results in a micro-mechanical model of a two-phase loop (Ricard et al., 2009), we predict QK-1 and Qμ-1 significantly higher than the PREM values for both body waves and normal modes. This attests that the olivine-wadsleyite transition can significantly contribute to the attenuation of the Earth's mantle transition zone.

  10. 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 T