Technical Report ECOM-01338-5 January 1968 STUDY OF POLYTYPIC PHASE RELATIONS AMONG COMPLEX INORGANIC STRUCTURES Semi-Annual Report For the Period 1 May 1967 to 31 October 1967 Report Noo 5 Contract No. DA 28-043 AMC-01338(E) Order No. FR 28-043-R5-20330(E) Prepared by Donald Ro Peacor The University of Michigan Department of Geology and Mineralogy Ann Arbor, Michigan for United States Army Electronics Command, Fort Monmouth, N J. This document has been approved for public release and sale; its distribution is unlimited.

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ABSTRACT The structure of the phase 2PbO.Fe203, corresponding to hematophanite, and coexisting with plumboferrite in the system PbO-Fe203, has been determined to be a derivative of the perovskite structure. Relations with several other structure types are described. The superstructure of plumboferrite has been redefined and the final results of the senaite structure determination are given. Progress on the construction and setup of a furnace for phase synthesis is reviewed. iii

REVIEW OF WORK COMPLETED PLUMBOFERRITE In Semi-Annual Reports Nos. 3 and 4 the plumboferrite crystal structure relations were described. Plumboferrite was shown to have a derivative structure relation to magnetoplumbite, and probably be hexagonal with unit cell parameters a = 10.20A and c = 23 45Ao The substructure (corresponding to the magnetoplumbite unit cell) has parameters a = 5 98A and c = 23~ 45A, as noted in previous reports. Crystals of plumboferrite have been subsequently re-examined with a-axis Weissenberg photography. The photographs clearly show that the superstructure has the dimensions a = 10.20A, c = 70.4A. This value of c is three times the previously reported value. The lattice is rhombohedral as compared with the previously reported primitive type. The discrepancy arose because of lack of resolution of adjacent levels in the previously available c-axis photographs. This result in no way changes the conclusions reached as given in Report No. 4 as regards the nature of the crystal structure. These conclusions were reached on the basis of substructure intensity values only, the relations for these being unchanged through redefinition of the supercell. The large supercell can be directly derived from the magnetoplumbite cell through suppression of translationso In addition, a degree of ordering is noted in the superstructure since, in rows along c, superstructure intensity values are alternately weak and strong. Attempts at deriving the superstructure on the basis of the previously defined substruct-ure and the new relations involving the superlattice have been unsuccessful, however. The detailed relations are only derivable with a determination of the full superstructure. Full three-dimensional intensity data are required for this from a crystal of well defined symmetry. We have continued to examine single crystals with a view to obtaining one which gave symmetrical relations among intensity valueso This continued search has been unsuccessful. The interpretation of this is that there is a high probability that crystals are twinned, at a scale such that the relative volumes of twin-related domains differ in different crystals. The total symmetry of the twin mosaic therefore differs from crystal to crystal. This interpretation is partially based on the fact that twinning is common in derivative structures such as that of plumboferrite, and is a normal feature of crystals showing pseudosymmetry. 1 THE UNIVERS TV ^W ~- ^ i ^?i-'

HEMATOPHANITE Mountvala and Ravitz (1962) have shown that, in the binary system PbO-Fe203, phases analogous to magnetoplumbite (the beta phase) and plumboferrite (the gamma phase) are stable in the subsolidus region. They are analogous to the naturally occurrin: phases except that each displays limited solid solution, not as yet detected in natural phases. However, a third phase (the delta phase) with a composition 2PbO Fe203 was characterized such that a field from about 33% to 67% Fe203 and 750 -910~C was occupied by two phase assemblage delta phase plus gamma phase. The delta phase was shown by powder photographic techniques to be tetragonal with a = -7079 and c = 15.85A, and to have eight formula weights per cell. We noted that this is identical with results obtained by Johansson (1928) for the naturally occurring phase hematophanite for which the formula 4PbOoPb(Cl, OH)2 2Fe203 was derived. The mineral hematophanite is known in only one circumstance, such that it occurs intimately associated with plumboferrite. Thus the mineral association is consistent with phase relations in the Fe203-PbO system. Since hematophanite is generally assumed to be related to the phases diaboleite, boleite, etc., and since these phases show large unit cells whose geometry indicates an origin in polytypic-like or unit cell t4winning relations, we have undertaken an investigation into the crystal chemistry of hematophanite. Recently collected specimens were kindly made available by Drm Paul Moore of the University of Chicago. Single crystal precession and Weissenberg photographs obtained on several crystals gave results which show that hematophanite is tetragonal withh unit cell parameters a =: 3 92A and c = 15o 31A These results are different than those quoted above in that one parameter is halved. There are no regular extinction rules so the possible space groups are P4/mmm. P42m, P4mm, P422, or P4m2. There is a very prominent superstructure such that the subcell has a translation of c/4 or 3.83A. Since this parameter is approximately equal to the value of a (3.92A) the subcell is pseudocubico The superstructure intensity values also display a less prominent subcell translation of c/2 (7.66A). The unit cell contents were calculated to be Pb3. 58M3~ 3508 8oHo, 88 Cl o. 67 where M is largely ferric iron with minor amounts of Na, K, Ca, Mg, Mn and Ti. The formula normalized to four lead atoms per cell (assuming an error in specific gravity) is Pb4M3.708~ 9OH. 99ggClo This may be idealized to Pb4Fe409 (OH, C1)2. On the assumption that crystals were untwinned (not uncommon with crystals with superstructures, and consistent with the observed holohedral diffraction symmetry) complete three-dimensional intensity data were 2

determined for the asymmetric unit of reciprocal space, processed for correction factors, and used for the computation of a Patterson synthesis P(uvw), as preparation for the determination of the structure. The structure was initially predicted on the following basis. Alpha PbTiO3 is cubic with a = 3.96A, and has the perovskite (CaTiO3) structure. This unit cell dimension corresponds to the cubic subcell parameters of hematophanite. In addition the ideal cell contents, PbFeO2.25(OH,Cl).5, are close to those of pervoskite. Thus we predicted that hematophanite has a structure which is derivative of that of perovskite. The superstructure arises through ordered substitution of OH and C1 for 0 with charge balance maintained through simultaneous formation of ordered anion vacancies. The Patterson synthesis showed peaks which displayed the translational periodicity of the substructure, and which were consistent with the perovskite structure. Thus the predicted structure relations were verified. We are now attempting to refine this structure in order to determine the'anion and vacancy ordering relations. Despite the fact that hematophanite has a cubic substructure, it displays a perfect (001) cleavage. This clearly is consistent with ordered anion vacancies in the c-axis direction. Strunz (1957) classes hematophanite with diaboleite (Pb2CuC12(0H4)). This phase is tetragonal, with a = 5.84, c = 5.47A. (Bystrom and Wilhemi, 1950). These parameters are approximately 42 times those of hematophanite, and the formula corresponds to that of perovskite type structures (A2B206) with half of the B cations missing. We have re-examined the structure determined by Bystrom and Wilhemi and find that it can, in fact, be viewed as a derivative of that of perovskite. It is derived through substitution of OH and C1 for 0 with charge vacancies, from their ideal perovskite structure positions. Cumengeite (PbloCuloCl2o0 H2o-H20; a = 14.9 A, c = 24.2a) pseudoboleite (PbloCusCl2o(OH)2o 5H20; a = 15.4 A, c = 31.2A) and boleite (PbloCusAg2, C1120H16-3H20; a = 15.4 A, c = 62. OA) all have large unit cells with parameters which are multiples of those of diaboleite (Ito, 1950) it is clear that their structures are all derivative to that of perovskite or hematophanite, at least in part. Subbareo (1962) has shown that there is a series of mixed layer compounds of general formula (Bi202) (MemlRmOmi) which are formed through the stacking of Bi202 and perovskite layers. These ferroelectric materials have lattice parameters similar to those of the phases related to diaboleite. The hematophanite structure thus appears to provide an insight into structural relations among a broad group of structures. 35

PHASE SYNTHESIS In order to synthesize phases at high temperature whose structural and chemical relations have been defined through our x-ray structures investigations, we have spent several months in the construction of a furnace. This device is now almost complete and will be ready for use shortly. The furnace was constructed using a platinum resistance heating coil such that the upper temperature limit is 1400-1500C as set by vaporization of platinum, with a stability of about +5~C. The sample size may be as great as 1-1/2 in. x 7 in., so that a cold-seal bomb may be used as a specimen container in order to achieve conditions of high pressure~ We have also independently constructed a power supply unit consisting of a voltage regulator and power stats. HIGH TEMPERATURE RELATIONS As noted in a previous proposal, we have available a unique furnace which we constructed for the single crystal diffractometer in order to determine x-ray intensity and reflection profile relations as a function of time and temperature. Of interest to this project are the stability relations as a function of temperature of polytypes. CaSi03 is known to occur as the polytypes wollastonite and parawollastonite in nature, although the latter phase has not been synthesized. In addition, disordered structures, intermediate to the above well ordered polytypes are also known. We have obtained specimens of CaSiO3 from a variety of sources. Each of these has been examined by single-crystal techniques in order to determine their nature as regards polytype variety. Single crystals having different ' degrees of stacking order have been characterized and specially mounted for the high temperature diffractometer. The high temperature order-disorder functions will thus be examined for these, and other materials, in the coming semi-annual period. SENAITE The crystal structure determination of senaite has been brought to a conclusion. The final result was obtained for space group R3 and refinement of the best model for this structure yeilded the R-factor of 21%. Atom coordinates for this model are listed in Table 1. The process of structure solution and a description of the principal structure features and their significance have been given in previous Reports and shall therefore not be further reviewed here. As noted in Semi-Annual Report 4, the agreement between observed and calculated structure factors is not as good as might be expected for a completely refined structure, although the R-factor noted above is in the 4

range normally indicative of a structure whose principal features are correctly defined. We have attempted, starting with the best models based on the centrosymmetric space group, to derive models based on space group R3. However, the agreement between structure factors does not improve sufficiently to warrant change in the original centrosymmetric model. We have found that our conclusions regarding basic relations among davidite, senaite and other complex oxides have been confirmed, in part, by Contag (1962). Although his conclusions have not been published, he duplicated our results regarding the basic chemistry and oxygen closest packing relations in these phases. The general relations between senaite, plumboferrite, magnetoplumbite and other phases are thus well documented. TABLE 1 Atom x x x Pb 0 0 0 0(1).2372.2955.0080 0(2) 5075 3912.9953 0(3) 3730.2611.1154 0(4).2733.4684.1028 0(5) o o o 0(6).2308.3064 o2264 0(7) 5375 3755 2253 M(l) 2/3 1/3.0231 M(2).4071 - 4257.0656 M(3).1841.1461.1656 M(4) 1/3 2/3 1/6 M(5) o 4176.4245.2750 AUTOMATED X-RAY EQUIPMENT Although this equipment was not purchased specifically for this project, and was in no way financed by this budget, it will be used in large part for it. We have obtained automation for the single crystal diffractometer and have been involved, in large part, with the debugging and setting up of this equipment, which is now completedo This will enable us to readily obtain intensity data on crystals which are under study for which the manually-obtained data is subject to questions of accuracy. Thus we plan on remeasuring data for senaite and nigerite in order to confirm and extend on conclusions previously arrived at with respect to these and other phases. THE UNlV'E pITY: M Mi 4 5~ ~ PI

LITERATURE CITED Bystrom, A. and K. A. Wilhemi (1950), The crystal structure of diaboleite, Pb2Cu(OH)4C12 Ark. Kemi 2, 397-404. Contag, Bodo (1962), Zur Kristallchemie von Davidite. Ph.D. Dissertation for the Berlin Technical University. Ito, T. (1950), X-Ray studies on Polymorphism. Maruzen Co., Tokyo. Johansson, K. (1928), Mineralogische Mitteilungen, Zeit. Krist. 68, 87-118. Mountvala, A. J., and Ravitz (1962), Phase relation and structures in the system PbO-Fe203. J. Am. Ceram. Soc. 45, 285-288. Shirane, G., S. Hoshino and K. Suzuli (1950), X-ray study of the phase transition in lead titanate, Phys. Rev. 80, 1105-1106. Strunz, Hugo (1957), Mineralogische Tabellen. Akademische Verlagsgesellschaft, Leipzig. Subbarao, E. C. (1962), Crystal chemistry of mixed bismuth oxides with layer-type structure. J. Am. Ceram. Soc. 45, 166-169. 6

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Unclassified Security Classification DOCUMENT CONTROL DATA - R&D (Security claaetication of title, body of abstract and indexing annotation must be entered when the overall report is classified) 1. ORIGINATING ACTIVITY (Corporate author) 2a. REPORT SECURITY C LASSIFICATION The University of Michigan UNCLASSIFIED Ann Arbor, Michigan 2b GROUP 3. REPORT TITLE STUDY OF POLYTYPIC PHASE RELATIONS AMONG COMPLEX INORGANIC STRUCTURES 4. DESCRIPTIVE NOTES (TYpo of report and Inctuive datee) Semi-Annual Report (1 May-1 Oct. 1967) S. AUTHOR(S) (LSet name. fint name, Initial) Peacor, Donald R. 6. REPO RT DATE 7. TOTAL NO. OF PAGE$S 7b. NO. OF REPF January 1968 6 8 ea. CONTRACT OR GRANT NO. 9a. ORIGINATOR'S REPORT NUMBER(S) DA 28-043-AMC-01338(E) Semi-Annual Report b. PROJC T NO. 072 lPO 14501 B11A 00 C. &b. OTHER REPORT NO(S) (Any other number that may be asslined 11. reportj d. |ECOM-01338-5 10. A V A IL ABILITY/LIMITAtION NOTICES This document has been approved for public release and sale; its distribution is unlimited. 11. SUPPLEMENTARY NOTES 12. SPONSORING MILITARY ACTIVITY U.So Army Electronics Command ATTN: AMSEL-XL-E Fort Monmouth, New Jersey 13. ABSTRACT The structure of 2PbO-Fe203, corresponding to the mineral hematophanite, and coexisting with plumboferrite in the PbO-Fe203 system, has been determined to be a derivative of the perovskite structure. Relations with other structure types, e.g., diaboleite, cumengeite, pseudoboleite, boleite, and a ferroelectric mixed-layer series involving Bi202 and perovskite layers, are described. The superstructure of plumboferrite has been redefined and its relation to magnetoplumbite clarified. Final results of the senaite structure determination are presented. Progress on the construction of a furnace for phase synthesis is reviewed. DD 1AN4 1473 Unclassified Security Classification

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