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Natural zeolites: odd genesis, intrinsic beauty, wide applications

Natural zeolites: odd genesis, intrinsic beauty, wide applications. Zelimir Gabelica. LPI-GSEC, ENSCMu, Mulhouse, France. Acknowledgments :. Dr Ermanno GALLI. Dr Sabine VALANGE. Mr Eddy VANDERMEERSCHE. Dr Roger WARIN. Mr Toni WIELAND. 2 nd FEZA School, Paris, September 1-2, 2008.

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Natural zeolites: odd genesis, intrinsic beauty, wide applications

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  1. Natural zeolites: odd genesis, intrinsic beauty, wide applications Zelimir Gabelica LPI-GSEC, ENSCMu, Mulhouse, France Acknowledgments: Dr Ermanno GALLI Dr Sabine VALANGE Mr Eddy VANDERMEERSCHE Dr Roger WARIN Mr Toni WIELAND 2nd FEZA School, Paris, September 1-2, 2008

  2. ZEOLITE GROUP Reference: Fleischer’s Glossary of Mineral Species M.E. Back & J.A. Mandarino, Miner. Rec. Ed., Tuscon (AZ), 2008, 345 pp MINERAL GROUPS A mineral group, consisting of at least 3 species, involves members having similar chemical formulae and, ideally, the same general structure, thus belonging to the same crystal system (not often respected) ZEOLITE GROUPS (Alumino)silicates (“and related”?) with framework structures containing open cavities in the form of channels and cages, usually occupied by H2O and extra-framework (charge-compensating) cations. Crystallography varies within the group. 90 officially recognized species (as for August 2008, including Direnzoite) are partitioned between series species and non-series species 1

  3. SERIES Seriescan be defined on the basis of dominant extra-framework cations In the case of zeolites, series were established for 15 generic species, each involving 2 or more species: BRE (Monoclinic): Ba, Sr  Ex: Brewsterite-Ba CHA (Trigonal): Na, K, Ca, Sr Note: Herschellite (discredited) Chabasite-K CLI (Monoclinic): Na, K, Ca DAC (Monoclinic): Na, Ca ERI (Hexagonal): Na, K, Ca FAU (Cubic): Na, Ca, Mg Note: Kaiserstuhl: presence of both FAU-Na &FAU-Mg FAU-Caexclusively found at Vogelsberg 2

  4. SERIES FER (Orth. & Mon.): Na, K, Mg GME (Hexagonal): Na, K, Ca HEU (Monoclinic): Na, K, Ba, Ca, Sr LEV (Trigonal): Na, Ca MAZ (Hexagonal): Na, Mg Note: Mt Semiol = Mazzite-Mg; Mazzite-Ca = Boron (CA) PAU (Cubic): K, Ca PHI (Monoclinic): Na, K, Ca STI (Monoclinic): Na, Ca THO (Orthorhombic): Ca, Sr Total: 41 valid species 3

  5. 49 OTHER NON-SERIES ZEOLITE SPECIES From Analcime to Yugawaralite … Some remarks: - Analcime: 5 different crystal systems: Cub., Tet., Orth., Mon., Tric. - Leucite (and Ammonioleucite) do belong to the zeolite group, but not their analog Sodalite (see later “Sodalite Subgroup” of CAN-SOD Group) - Barrerite (Orthorhombic) is different from Stilbite-Na (Monoclinic) - 3 Li-bearing species: Bikitaite, Hsianghualite, Pahasapaite - 5 Beryllosilicate frameworks: Chiavennite, Hsianghualite, Lovdarite, Nabesite, Roggianite - 2 Beryllophosphate frameworks: Pahasapaite, Weinebeneite (Tiptopite = Cancrinite sub-group) 4

  6. 49 OTHER NON-SERIES ZEOLITE SPECIES From Analcime to Yugawaralite(continued) - 1 Zincosilicate framework: Gaultite (Na4Zn2Si7O18.5H2O, Orth.) - Kalborsite: contains 2 “extra-framework” anions: B(OH)4- and Cl- - Tschörtnerite: contains 1extra-framework exotic” anion: Cu(OH)82- - Presence of (framework?) cations other than alkali or alkaline-earth: Maricopaite (framework Pb(O,OH)4) and Chiavennite (Mn2+) - Highest Si/Al ratios: Mutinaite (7.73), Gottardiite (7.31) - Status of Phosphovanadylite ?? (Na,K,Ba,Ca-aluminovanadophosphate) 5

  7. CANCRINITE-SODALITE GROUP Divided into 3 sub-groups, based on the stacking sequence of layers of non-connected 6MR: 29 species - Cancrinite sub-group: Trigonal or hexagonal species involving “cancrinite cages” Containing salts (ionic pairs: Na, Ca, Cl…) that fill the void space 10 species Ex: cancrinite, cancrisilite, davyne, tiptopite…) - Sodalite sub-group: Cubic or tetragonal species involving cuboctahedral “sodalite cages” Filled with clusters of atoms (cations, SO4, Cl, (poly)sulphides…) 11 species Ex: Sodalite (Cl), Lazurite (S, Cl, OH), Haüyne (SO4), Genthelvite (Fe & S), Helvine (Mn & S) … 6

  8. CANCRINITE-SODALITE GROUP - Sodalite sub-group: (continued) NB: Tsaregorodsevite (TMA)4[Si2(Si0.5Al0.5)O6]2, involves TMA+ cations that (probably) act as both structure-directing agents (SOD cages) and counterions to one framework negative charge. - Other species in the CAN-SOD group: Trigonal or hexagonal species with different stacking sequences: 8 species Ex: Afghanite, Franzinite, Giuseppetite, Liottite … 7

  9. RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 8

  10. RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 9

  11. RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 10

  12. RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 11

  13. RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 12

  14. RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 13

  15. RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 14

  16. NEW TOPOLOGIES ? 15

  17. NEW TOPOLOGIES ? 16

  18. NEW TOPOLOGIES ? 17

  19. “ZEOLITHE INFAILLIBLE” : FIRST APPLICATION ? 18

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