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Conversion of Perovskite to Anatase and Tio2

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Conversion of Perovskite to Anatase and Tio2 American Mineralogist, Volume 77, pages 545-557, 1992 Conversionof perovskite to anataseand TiO2 (B): A TEM study and the use of fundamentalbuilding blocks for understandingrelationships among the TiO, minerals Jrr.r.r.lN F. BlNrrnr,Drt Dlvro R. VBnr,rN Department of Earth and Planetary Sciences,The Johns Hopkins University, Baltimore, Maryland 21218, U.S.A. Ansrucr TiO, crystallizes in at least seven modifications encompassingseveral major structure types including those of rutile, hollandite, and PbOr. We have adopted a fundamental building block (FBB) approach in order to understand better the relationships between these structures.The identification of common structural elementsprovides insights into possiblephase transformation mechanismsas well as the weatheringreactions that convert perovskite (CaTiOr) to TiO, anataseand TiO, (B). We have studied the weathering of perovskite from the Salitre II carbonatite, Minas Gerais, BraziI, by transmission electron microscopy. Although the dissolution of perov- skite, a proposed component of the high-level nuclear waste form Synroc, has been mod- eled thermodynamically and studied experimentally, its direct natural replacementby Ti oxides during weathering has not been previously described. Our results show that the perovskite is replaced topotactically by both anataseand TiO, (B). The reaction appears to involve an intermediate product that can be interpreted as a half-decalcified,collapsed derivative of perovskite. The second step, involving removal of the remaining Ca, can occur in one of two ways, leading either to anatase or in rare casesto TiO, (B). The orientations of the interfaces between both perovskite and anataseand perovskite and TiO, (B) are consistent with collapse of the corner-linked Ti-O framework to form edge- sharing chains. Despite the orthorhombic structure of perovskite, the resultsshow that the anatase can develop with its c axis parallel to any of its three pseudocubic axes. The complete destruction of perovskite produces arrays primarily of anatasethat display a variety of textures, including porous aggregatesand recrystallized needles.REE elements releasedfrom perovskite are immobilized by precipitation of rhabdophane that is inti- mately intergrown with anatase. INrnonucrroN is related to the rutile structure by a second-orderphase There are currently four naturally occurring TiO, poly- transformation (discussed by Hyde, 1987). The high- pressure polymorph, morphs [rutile, anatase,brookite, and TiO, (B)] and at TiO, II, has the a-PbO, structure; least three (plus some very high-pressureforms) poly- the highly metastable TiO, (H) polymorph has the hol- morphs that have been produced synthetically. Details landite structure; and TiO, (B) has a structure that is for six of the distinctive polymorph structures are listed closely related to that of VO, (B). The similarities be- in Table I . It is generallyconsidered that at low pressures tween some of these polymorphs and the related struc- only rutile has a true field of stability; anataseand brook- tures of anataseand brookite will be discussedbelow. ite form metastably(Dachille et al., 1968; Post and Burn- All of the polymorphs contain edge-and corner-linked, ham, 1986).Post and Burnham (1986) used ionic mod- octahedrally coordinated Ti cations. The available struc- eling to show that the electrostatic energies of rutile, ture refinements(see asterisks in Table l) show relatively anatase,and brookite are not greatly different. Navrotsky constant Ti-O distancesand quite variable O-O distanc- and Kleppa (1967) measuredAH : -5.27 kJlmol for the es, particularly when the shared vs. unshared octahedral anataseto rutile reaction. edgesare compared.Pairs offace-sharing octahedra(con- The structureof the most commonly occurringand best taining trivalent Ti) are found only in crystallographic known TiO, phase,rutile, is sharedby a number of min- shear structuresin reduced rutile derivatives (TiOr_.). erals including pyrolusite, cassiterite,stishovite, and in a Previous discussionsofthe relationships between cer- distorted form, marcasite.The CaCl, polymorph of TiO, tain of these structures have focused on the presenceof sheetsof O atoms that approach a cubic closest-packing * Present address: Department of Geology and Geophysics, arrangement(such as in anatase),very distorted hexago- University of Wisconsin-Madison, 1215 West Dayton Street, nal closest packing that approachescubic (as in rutile; Madison,Wisconsin 53706, U.S.A. Hyde et al.,1974), or an approximately double hexagonal ooo3404x/ 9210506-0545$02.00 545 546 BANFIELD AND VEBLEN: PEROVSKITE TO ANATASE AND TiO, (B) TaBLE1. Data for some TiO2polymorphs and perovskite Density Unit-celldata Structure Space group (g/cm") (nm) Reference Rutile' P4"lmnm 4.13 a : 0.459,c: 0.296 Cromer and Herrington(1955) Anatase* Allamd 3.79 a : 0.379,c: 0.951 Cromer and Herrington(1955) Brookite' Pbca 3.99 a : 0.917,b : 0.546,c : 0.514 Baur(1961) Tio, (B) C2lm 3.64 a : 1.2'16,b : 0.374,c : 0.651,0 : 1O7.2V Marchand et al. (1980) Tio, il' Pbcn 4.33 a : 0.452.b : 0.550.c : 0.494 Simonsand Dachille(1967) Tio, (H) Alm 3.46 a : 1.018,c: 0.297 Latroche et al. (1989) Perovskite" Pcmn 4.03 a: 0.537.b: 0.764,c: 0.544 Kay and Bailey(1957) * Structures refined by X-ray ditfraction. closest-packingarrangement (as in brookite). These de- tal building blocks (FBB; Moore, 1986),emphasizes the scriptions emphasizedifferences among the structuresbut similarities betweenthe structures.The aim is to provide fail to highlight their close relationships. insights into possible direct mechanismsby which poly- Andersson (1969) showed that rutile could convert to morphic phasetransformations involving TiO, might oc- the TiO, II structure by cation displacement.Simons and cur. We discuss the application of this view to under- Dachille (1970) noted that similar structural elementsare standing the TiO, (B)-anatase transformation. In the presentin anataseand TiO, II and suggestedthat a trans- second part of this paper we use the FBB description as formation between cubic closest-packedand hexagonal well as experimental results to describe perovskite closest-packedarrangements involves shear between O (CaTiOr)-TiO, weathering reactions. Iayers. Bursill and Hyde (1972) and Hyde et al. (1974) de- AN FBB APPROACHTO THE STRUCTURAL scribed a relationship betweenhollandite and rutile struc- RELATIONSHIPS BETWEEN RUTILE, ANATASE' (B), (H) tures involving rotation of adjacent rutile blocks by BRooKrrE, TiO, aNo TiO' clockwise and counterclockwise rotation. Alternatively, There are many ways to describe structures and the Bursill (1979) demonstratedthat the hollandite structure relationships between them. For example, the utility of can be generatedfrom the rutile structure by intersecting the polysomatic-seriesapproach has been discussedin antiphase boundaries or crystallographicshear. Latroche detail by Veblen (1991). Although this structuralratio- et al. (1989) reportedthat the TiO, (H) polymorph con- nalization works well for many minerals, it cannot be verted to anataserather than rutile with increasingtem- simply applied to describethe TiO' polymorphs, primar- perature and noted that the structural relationship be- ily becauseof the absenceof slabs common to all poly- tween TiO, (H) and anatasewas not clear. morphs. As noted in the introduction, both crystallo- The dissolution of perovskite and its replacement by graphic shear models and descriptions based upon the TiO, has been studied experimentally under a range of geometry of the O framework have been used to describe hydrothermal conditions (e.g.,Myhra et al., 1984; Kas- and relate some of the TiO, structures.In this discussion, trissioset al., 1986,1987; Jostsons et al., 1990).The in- we take a rather different approach. Following Moore terest is partly due to the proposal that perovskite could (1986),we describethe TiO, structuresin terms of their be a major component of the synthetic assemblageof construction from a single structural unit, or FBB, by titanate minerals known as Synroc, a potential nuclear either direct assembly or shear. This approach reveals waste form. Thermodynamic calculations have clearly both the close relationships (some groups of TiO, poly- shown that perovskite is unstable with respect to both morphs contain common structural layers) and the dif- titanite and rutile at low temperaturesand in natural wa- ferencesbetween members of the group (e.g.,in the stack- ters (Nesbitt et al., l98l). Kastrissioset al. (1987) sug- ing ofthese layers). gestedthat perovskite dissolvedunder hydrothermal con- FBB ditions (between ll0 and 190 "C) and that euhedral Choice of an anatase and brookite crystals grew epitaxially from an The attempt to use an approach basedon the presence amorphousTi-O layer.Jostsons et al. (1990)summarized of common structural elements in the TiO, polymorphs much of the experimental work on perovskite dissolution was hampered by two problems. First, the largest struc- including data ofPham et al. (unpublished data), which tural block common to all of them is merely a pair of suggestthat under epithermal conditions (<80 "C) an edge-sharingoctahedra. Second, the group of TiO, struc- amorphousTi-rich layer approximately l0 nm thick forms tures falls into two categories,namely, those that contain on the perovskite surface.This layer is believed to incor- chains ofedge-sharingoctahedra in one orientation [TiO, porate Ca ions and act as a protective barrier that inhibits (B), anatase]and those with chains in two orientations
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