Browsing by Author "Cashion, JD"

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    Fe speciation in geopolymers with Si/Al molar ratio of ~2.
    (Elsevier, 2007-05-01) Perera, DS; Cashion, JD; Blackford, MG; Zhang, Z; Vance, ER
    The speciation of Fe was studied in metakaolin-based geopolymers to which Fe was added as ferric nitrate solution or freshly precipitated ferric hydroxide. From Mössbauer and near-edge X-ray absorption spectroscopies, coupled with X-ray diffraction and electron microscopy, it was concluded that in as-cured geopolymers the Fe was present in octahedral sites, either as isolated ions in the geopolymer matrix or as oxyhydroxide aggregates which had not reacted with the starting geopolymer components. For material to which iron nitrate was added, heating to 900°C allowed the formation of nepheline and a glass, both of which contained tetrahedrally coordinated, substituted Fe3+. © 2007, Elsevier Ltd.
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    Freudenbergite - a new example of electron hopping
    (Australian Institute of Physics, 2014-02-06) Cashion, JD; Lashtabeg, A; Vance, ER; Ryan, DH; Solano, J
    Mössbauer spectra of freudenbergite samples with different composition have showed that although the Fe and Ti populate the octahedra randomly, Fe prefers the M(1) site over the M(2) site by approximately 1.3:1. Ti was able to accommodate mixed valence more easily than Fe, but some samples showed dynamic electron hopping in the Fe ions, which also affected the diffuse reflectance in the 400-800 nm region.
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    Mössbauer study of the temperature dependence of electron delocalization in mixed valence freudenbergite
    (John Wiley & Sons, Inc., 2020-05-04) Cashion, JD; Vance, ER; Ryan, DH
    The evolution of the electron delocalization in the ferrous subspectra in a sample of mixed valence ferrous‐ferric freudenbergite has been followed by Mössbauer spectroscopy from 6 K to 650 K. The spectral changes do not involve the ferric component, leading to the conclusion that it is due to a thermally driven delocalization of the sixth d‐electron on the ferrous ions. The phenomenon does not occur in samples of pure ferrous freudenbergite. © 1999-2020 John Wiley & Sons, Inc.
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    The rockbridgeite group approved and a new member, ferrorockbridgeite, (Fe2+,Mn2+)2(Fe3+)3(PO4)3(OH)4(H2O), described from the Hagendorf Süd pegmatite, Oberpfalz, Bavaria
    (Schweizerbart Science Publishers, 2019-06-06) Grey, IE; Kampf, AR; Keck, E; Cashion, JD; MacRae, CM; Gozukara, Y; Peterson, VK; Shanks, FL
    The rockbridgeite group has been officially established by the IMA Commission on New Minerals, Nomenclature and Classification. The general formula is based on the structure and is A 2 B 3(PO4)3(OH, H2O)5, where A = the octahedrally coordinated M2 site, in which divalent cations are ordered, and B = the octahedrally coordinated M1 + M3 sites, which contain predominantly Fe3+, with trace Al. The different rockbridgeite-group minerals are distinguished by the occupancy of the A site. The ideal formula for rockbridgeite is F e 0.5 2 + Fe 0.5 3 + 2 Fe 3 3 + PO 4 3 OH 5 , that for frondelite is Mn 0.5 2 + Fe 0.5 3 + 2 Fe 3 3 + PO 4 3 OH 5 and that for plimerite is Z n 2 Fe 3 3 + P O 4 3 OH 4 ( H 2 O ) . In order to preserve the identity of frondelite and rockbridgeite within the structure-based formalism, these species correspond to mid-series compositions. We describe here the new end-member, ferrorockbridgeite, with dominant Fe2+ in the A site, from the Hagendorf Süd pegmatite mine, Oberpfalz, Bavaria. Electron microprobe analyses, coupled with Mössbauer spectroscopy, gives the empirical formula Fe 1.33 2 + Mn 0.52 2 + Zn 0.03 Ca 0.05 Fe 3.03 3 + Al 0.01 P 2.97 H 6.17 O 17 . The simplified formula is F e 2 + , M n 2 + 2 F e 3 3 + P O 4 3 OH 4 ( H 2 O ) . Ferrorockbridgeite is orthorhombic, space group Bbmm, with a = 13.9880(4), b = 16.9026(5), c = 5.1816(1) Å, V = 1225.1 Å3 and Z = 4. The six strongest lines in the X-ray powder diffraction pattern are [d meas/Å (I) (hkl)]: 4.853 (26) (101), 3.615 (24) (240), 3.465 (33) (301), 3.424 (39) (410), 3.205 (100) (321) and 1.603 (24) (642). Optically, ferrorockbridgeite is biaxial (–) with α = 1.763(3), β = 1.781(calc), γ = 1.797(3) (white light) and 2V (meas.) = 87(1)° from extinction data. The optical orientation is X = c, Y = a , Z = b. The pleochroism is X = blue green, Y = olive green, Z = yellow brown; X ≈ Y > Z. The rockbridgeite group has been officially established by the IMA Commission on New Minerals, Nomenclature and Classification. The general formula is based on the structure and is A 2 B 3(PO4)3(OH, H2O)5, where A = the octahedrally coordinated M2 site, in which divalent cations are ordered, and B = the octahedrally coordinated M1 + M3 sites, which contain predominantly Fe3+, with trace Al. The different rockbridgeite-group minerals are distinguished by the occupancy of the A site. The ideal formula for rockbridgeite is F e 0.5 2 + Fe 0.5 3 + 2 Fe 3 3 + PO 4 3 OH 5 , that for frondelite is Mn 0.5 2 + Fe 0.5 3 + 2 Fe 3 3 + PO 4 3 OH 5 and that for plimerite is Z n 2 Fe 3 3 + P O 4 3 OH 4 ( H 2 O ) . In order to preserve the identity of frondelite and rockbridgeite within the structure-based formalism, these species correspond to mid-series compositions. We describe here the new end-member, ferrorockbridgeite, with dominant Fe2+ in the A site, from the Hagendorf Süd pegmatite mine, Oberpfalz, Bavaria. Electron microprobe analyses, coupled with Mössbauer spectroscopy, gives the empirical formula Fe 1.33 2 + Mn 0.52 2 + Zn 0.03 Ca 0.05 Fe 3.03 3 + Al 0.01 P 2.97 H 6.17 O 17 . The simplified formula is F e 2 + , M n 2 + 2 F e 3 3 + P O 4 3 OH 4 ( H 2 O ) . Ferrorockbridgeite is orthorhombic, space group Bbmm, with a = 13.9880(4), b = 16.9026(5), c = 5.1816(1) Å, V = 1225.1 Å3 and Z = 4. The six strongest lines in the X-ray powder diffraction pattern are [d meas/Å (I) (hkl)]: 4.853 (26) (101), 3.615 (24) (240), 3.465 (33) (301), 3.424 (39) (410), 3.205 (100) (321) and 1.603 (24) (642). Optically, ferrorockbridgeite is biaxial (–) with α = 1.763(3), β = 1.781(calc), γ = 1.797(3) (white light) and 2V (meas.) = 87(1)° from extinction data. The optical orientation is X = c, Y = a , Z = b. The pleochroism is X = blue green, Y = olive green, Z = yellow brown; X ≈ Y > Z. The rockbridgeite group has been officially established by the IMA Commission on New Minerals, Nomenclature and Classification. The general formula is based on the structure and is A 2 B 3(PO4)3(OH, H2O)5, where A = the octahedrally coordinated M2 site, in which divalent cations are ordered, and B = the octahedrally coordinated M1 + M3 sites, which contain predominantly Fe3+, with trace Al. The different rockbridgeite-group minerals are distinguished by the occupancy of the A site. The ideal formula for rockbridgeite is F e 0.5 2 + Fe 0.5 3 + 2 Fe 3 3 + PO 4 3 OH 5 , that for frondelite is Mn 0.5 2 + Fe 0.5 3 + 2 Fe 3 3 + PO 4 3 OH 5 and that for plimerite is Z n 2 Fe 3 3 + P O 4 3 OH 4 ( H 2 O ) . In order to preserve the identity of frondelite and rockbridgeite within the structure-based formalism, these species correspond to mid-series compositions. We describe here the new end-member, ferrorockbridgeite, with dominant Fe2+ in the A site, from the Hagendorf Süd pegmatite mine, Oberpfalz, Bavaria. Electron microprobe analyses, coupled with Mössbauer spectroscopy, gives the empirical formula Fe 1.33 2 + Mn 0.52 2 + Zn 0.03 Ca 0.05 Fe 3.03 3 + Al 0.01 P 2.97 H 6.17 O 17 . The simplified formula is F e 2 + , M n 2 + 2 F e 3 3 + P O 4 3 OH 4 ( H 2 O ) . Ferrorockbridgeite is orthorhombic, space group Bbmm, with a = 13.9880(4), b = 16.9026(5), c = 5.1816(1) Å, V = 1225.1 Å3 and Z = 4. The six strongest lines in the X-ray powder diffraction pattern are [d meas/Å (I) (hkl)]: 4.853 (26) (101), 3.615 (24) (240), 3.465 (33) (301), 3.424 (39) (410), 3.205 (100) (321) and 1.603 (24) (642). Optically, ferrorockbridgeite is biaxial (–) with α = 1.763(3), β = 1.781(calc), γ = 1.797(3) (white light) and 2V (meas.) = 87(1)° from extinction data. The optical orientation is X = c, Y = a , Z = b. The pleochroism is X = blue green, Y = olive green, Z = yellow brown; X ≈ Y > Z. © 2018 E. Schweizerbart’sche Verlagsbuchhandlung
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    Temperature dependence of electron delocalization in mixed balance freudenbergite
    (Australian Institute of Physics, 2020-02-04) Cashion, JD; Vance, ER; Ryan, DH
    Since our last reports, we have carried out further experiments on the mixed valence sodium iron-titanate freudenbergite [1, 2]. Freudenbergite has the nominal formula Na2FexTi8-xO16, with x = 1 being ferrous and x = 2 being ferric. However, a ferrous composition sample, calcined in air, became mixed valence with a closely 50:50 valence split. It is normally considered that the Fe and Ti ions are randomly distributed in the two (Fe,Ti)O6 octahedra. However neutron diffraction showed that the Ti:Fe ratio was 0.82:0.18 in the larger M(1) site and 0.93:0.07 in the smaller M(2) site compared to the average 0.875:0.125. It is expected that all the iron in the smaller M(2) site will be ferric. The sample turned out to have very unusual Mössbauer spectra as the temperature was varied. At low temperatures, well resolved ferric and ferrous doublets were observed. But as the temperature was increased, the ferrous doublet slowly collapsed and had to be fitted with up to three doublets to match the envelope. The ferric doublet remained unchanged in intensity and hyperfine parameters. The collapse of the ferrous spectrum is due to a thermally driven electron delocalization of the sixth d-electron. The electric field gradient in ferrous materials is mainly due to this electron and its removal causes the quadrupole splitting to more closely resemble that of the ferric ions, which is due entirely to the lattice. We have tried unsuccessfully to manufacture more of these electron mobile samples with various compositions and calcining in air and argon. However, pure ferrous and pure ferric samples do not display any dynamic behaviour, and even a ferrous sample with 3% ferric iron did not display any dynamics [2]. Spectra of the present sample taken at 6K and 10 K showed evidence of broadening, presumably due to the inset of magnetic ordering. However, it was not clear whether both ions were ordering or only one. There is no record of a magnetic ordering temperature for freudenbergite in the literature, and any such observation will undoubtedly be strongly sample dependent. The electron dynamics can be caused by intervalence charge transfer between ions or by crystal field effects or electron delocalisation in single ions, and are the primary cause of the colour in popular minerals. Other Fe-Ti minerals which exhibit such behaviour in the Mössbauer spectra include sapphire, kyanite, fassaite, omphacite, aenigmatite, and Ti andradite.