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J. Am. Ceram. Soc., 83  605–11 (2000)
Crystal Structure and Related Properties of Manganese-Doped Barium Titanate Ceramics
Hans Theo Langhammer,† Thomas Muller,‡ Karl-Heinz Felgner,† and Hans-Peter Abicht‡ ¨
Departments of Physics and Chemistry, Martin-Luther-Universitat Halle-Wittenberg, D-06099 Halle, Germany ¨ The influence of manganese on the crystallographic phase and the microstructure of BaTi1 xMnxO3 ceramics (0 < x < 0.05) is investigated. The crystal structure at room temperature changes from tetragonal to hexagonal between x 0.005 and 0.017, which causes a drastic change in the microstructure. 3 The Jahn–Teller distortion caused by the MnTi ions is proposed as the driving force for the phase transition. Annealing of the as-fired samples in both a reducing and oxidizing atmosphere restores the tetragonal phase, which is accompanied by a change in the microstructure based on the percentage of tetragonal phase. I. Introduction sufficient to stabilize h-BT at room temperature. Recnik and ˘ Kolar14 –16 also investigated the microstructure of h-BT sintered at 1360°C in a H2/Ar atmosphere and found strongly exaggerated grain growth, which leads to large platelike hexagonal grains. Doping with 3d transition elements, such as manganese, iron, or nickel, is the second way of stabilizing h-BT at room temperature.8,17–22 Because of their small ionic radii, they substitute for Ti4 , which is commonly accepted in the literature. Their valence state when they are incorporated into the lattice has been discussed in numerous experimental and theoretical papers. In the case of manganese,2,24 –27 Glaister and Kay8 found that it is the most effective dopant for stabilizing h-BT. Dickson et al.,17 and recently Takeuchi et al.,12 proposed a chemical bonding between the two d orbitals of titanium and manganese as a reason for stabilization of the face-sharing TiO6/MnO6 octahedra in h-BT. Ren et al.19 stated that the small size of the Mn4 ion, which substitutes Ti4 , is a dominant factor favoring the formation of h-BT. A critical discussion of this assumption was published by the authors of the present paper.20 Similar to h-BT produced by sintering in reducing atmosphere, manganese-doped h-BT also exhibits a pronounced exaggerated growth of platelike grains.20,21 Comparing the published results, the whole picture of manganese-doped BaTiO3 is not quite clear. This is true for both the microscopic models describing the phase transition from cubic/tetragonal to hexagonal and also macroscopic properties, such as quantitative phase composition, depending on the doping level and the parameters of the sintering process or the microstructure formed. One reason for the inconsistency of the macroscopic results seems to be the strong influence of impurities of the raw materials on the phase composition and microstructure. As an example, the influence of strontium as an impurity is discussed in a subsequent paper.28 Hence, the aim of this paper is to clarify the influence of manganese on the macroscopic properties of BaTiO3 ceramics mentioned above (crystallographic phase, microstructure) as well as discuss the microscopic mechanism of the phase transition from cubic to hexagonal and the role of manganese in the promotion of this process. For this purpose, we performed detailed investigations of manganese-doped BaTiO3 at a doping level of between 0 and 5 mol% with regard to the following properties: X-ray diffraction (XRD), electron diffraction, microstructure, and the solubility of manganese in the BaTiO3 lattice. Both as-sintered specimens and samples annealed in oxidizing and reducing atmospheres were investigated. II. Experimental Procedure
ANGANESE-DOPED BaTiO3 ceramics are used for several purposes. The main applications are capacitors and devices using the positive temperature coefficient of resistance (PTCR), where, as an effective acceptor dopant, manganese influences both the electrical properties and the microstructure, because it is an effective acceptor dopant. In capacitor materials, manganese improves resistivity to reducing atmospheres during sintering. In donor-doped PTCR ceramics, manganese depresses the grain size and enhances the rise in electrical resistivity near the Curie temperature of BaTiO3. Much work has been done to elucidate the role of manganese regarding these effects.1–7 However, little is known about the influence of manganese on the crystallographic structure and the microstructure of otherwise undoped BaTiO3. Glaister and Kay8 first reported in 1960 that certain amounts of manganese are sufficient to stabilize the hexagonal phase of BaTiO3 (h-BT) at room temperature, whereas the hexagonal polymorph of undoped material is stable in air only at temperatures 1460°C.9,10 Two possibilities are known to stabilize h-BT at lower temperatures. The first one is firing in reducing atmospheres.8,11–16 In pure hydrogen, a temperature of 1330°C is sufficient to stabilize the hexagonal phase.8 The formation of oxygen vacancies and the resulting reduction of Ti4 to Ti3 according to the reaction
2TiTi º VO
seems to be the generally accepted reason for this stabilization effect, which is explained by the preferred formation of facesharing octahedra (Ti2O9 groups), because of the reduced electrostatic repulsion between Ti3 and Ti4 /Ti3 ions compared with the interaction between Ti4 ions. According to Wakamatsu, Takeuchi, and co-workers,11,12 a minimum of 0.3 mol% of Ti3 is
B. M. Kulwicki—contributing editor
Manuscript No. 190362. Received February 20, 1998; approved July 23, 1999. Supported by the Kultusministerium des Landes Sachsen-Anhalt, Germany, and the Deutsche Forschungsgemeinschaft under Contract No. FKZ: 1434A/0083. † Department of Physics. ‡ Department of Chemistry.
Ceramic powder with a nominal composition of BaTi1-xMnxO3 (0 x 0.05) was prepared by the conventional mixed-oxide powder technique. After mixing (agate balls, water) and calcining (1100°C, 2 h) appropriate amounts of BaCO3 ( 0.1 mol% strontium; No. 3018, Leuchtstoffwerk Breitungen GmbH, Germany), TiO2, (No. 808, Merck, Darmstadt, Germany), and MnCO3 (Riedel de Haen, Germany), we fine-milled (agate balls, water) and densified the powder to disks with a diameter of 12 mm and a height of nearly 3 mm. Because of the thermodynamic instability of BaTiO3 in water, the Ba/Ti ratio of the green bodies amounted 605
(B) Annealed Samples: Whereas the samples annealed in air show no remarkable change in microstructure compared with the as-sintered specimens. The average grain sizes of all samples investigated are shown in Fig.16 reported on small cubic grains in undoped h-BT sintered in a reducing atmosphere. most remarkable finding is the nearly complete restoration of the tetragonal phase after annealing in reducing atmosphere at a manganese concentration of 1. and fluorescence excitation (ZAF) at higher manganese concentrations. and ion milling up to perforation of their central region. (B) Annealed Samples: The annealed samples show a significant effect of restoration of the tetragonal phase. an increasing number of manganese ions are not soluble in the BaTiO3 lattice of the platelike grains but segregate at grain boundaries or form intergranular manganese-rich phases that are clearly visible in the EPMA-measured distribution images of manganese. At 1. a portion of each sample was annealed in air and another portion was annealed in a gas stream mixture of H2 and argon (1/1). dimpling.5 and 5. 3. Only for manganese concentrations 3 mol%. Cameca Instruments. the percentage of which exceeds the percentage of the platelike fraction at a nominal manganese content of 5 mol%. the globular grains (diameter: 5–10 m) reappear. 3 to 1/1.5 mol%. mainly small grains were investigated by electron diffraction.0 mol%. During annealing in a highly reducing atmosphere. and characterized again. the samples were contained in ZrO2-covered Al2O3 dishes. the manganese content of which partially exceeds 7. An advantage of the method is also the possibility of local measurements. France) was performed. the effect is clearly more pronounced for reducing conditions.5 mol%.7 mol% seem to be completely in the hexagonal phase. In both cases. absorption. For the phase investigations at room temperature by XRD. Corresponding to Figs. Corbevoie. Karlsruhe.015. Only the percentage of tetragonal phase as a function of the doping level of manganese is shown. once again. (A) As-Fired Samples: The region of coexistence of the tetragonal and hexagonal phases in the as-fired samples lies between 0. A new grain type with a platelike shape and a grain size of 400 m develops. Results (1) X-Ray Diffraction The results of the XRD investigations both for the as-fired and annealed samples are shown in Fig.6 and 2. Below and above this region. wavelengthdispersive X-ray electron probe microanalysis (WDX-EPMA) (Model CAMEBAX. according to their considerable percentage of tetragonal phase (see Fig. which is especially pronounced for samples with manganese concentrations between 1. these grains have grown into each other during the final stage of sintering and their platelike shape is deformed. The small deviation of the integrally measured values from the nominal manganese content seems to be due to an uncertain correction of atomic number effect. Then.606 Journal of the American Ceramic Society—Langhammer et al. because it is not easy to distinguish between the hexagonal and cubic phase of BaTiO3 (c-BT) by XRD measurements. No. Figs. Hence. Kolar et al. which exhibit the globular shape of the manganese-free ceramics. Although this holds for both types of annealing atmospheres. Up to a manganese content of 0.29 The samples were sintered in air at Ts 1400°C for 1 h and subsequently characterized with respect to their microstructure and phase composition (see below). when the platelike grains are surrounded by a sufficient amount of small globular grains.6 mol% manganese. To avoid interfering contamination. Eindhoven. With increasing manganese content. the microstructure becomes bimodal. (4) Solubility of Manganese (A) As-Fired Samples: The results of our investigation into the solubility of manganese in BaTiO3 are shown in Fig. Simultaneously with the appearance of the hexagonal phase at 1 mol% manganese. annealing was accomplished at 1200°C in 2 h.%.7 mol% manganese. while the grains of the other fraction. XRD-determined percentage of tetragonal phase (20°C) as a function of the nominal manganese content (x) of BaTi1-xMnxO3 before and after annealing under both oxidizing and reducing conditions. Siemens Aktiengesellschaft. the remaining percentage corresponds to the hexagonal phase. because we used metallic manganese as a standard sample. 1. corresponding approximately to the disappearance of the tetragonal phase. To determine the distribution of manganese in the grains and intergranular regions. Therefore. Because of the similarities to the microstructure of the manganese-doped samples.5 and 1. Figure 4 shows the TEM image of some small grains of a sample with 5 mol% manganese together with a typical hexagonal electron diffraction pattern of one of these grains.5 mol%. 83. the smaller globular grains have vanished.0 mol%. If no other statement is given. the average grain sizes of which are also shown in Fig. 1). Samples for transmission electron microscopy (TEM) and electron diffractometry (Model CM20Twin. the samples are single-phase within the accuracy of the XRD method. None of the numerous grains investigated exhibited the cubic phase. the microstructure becomes bimodal. At lower manganese concentrations. and their percentage decreases. has not been successful thus far. The Netherlands) were thinned by consecutive mechanical grinding. which is not better than 2–5 mol%. Vol. 2(a)–(e). While the nominal amount of manganese is completely incorporated up to 1. some manganese is expelled from the specimens. The Fig. (3) Electron Diffraction Samples were characterized by electron diffraction. Identification of these phases. the sintered samples were crushed again and mixed with silicon powder for the purpose of calibration. 1. Philips. Germany). 2(f)–(j) show the microstructures of the hydrogen-annealed samples. The phase composition was determined quantitatively by analyzing the intensity ratios (111)tetragonal/(103)hexagonal and (200)tetragonal/(103)hexagonal using a diffractometer (Model D5000. probably all the samples investigated with a manganese content of 1. The microstructure of polished and chemically etched specimens was examined by optical microscopy and by scanning electron microscopy (SEM). the samples annealed in a highly reducing atmosphere exhibit a significant reduction in grain size and a change in the grain shape. . corrected data giving the remaining manganese concentration (see below) are also shown in Fig. 1. Two different phases III. for higher manganese concentrations. (2) Microstructure (A) As-Fired Samples: Figures 2(a)–(e) show microstructures of samples with a nominal manganese content of between 0. All heat treatments took place with heating and cooling rates of 10 K/min.5 at. is their platelike shape clearly developed. 3. the microstructure looks like the well-known microstructure of undoped liquid-phase-sintered BaTiO3 ceramics.6 mol%. For nominal manganese concentrations of 2. 5. become smaller.
(h) 0.030.March 2000 Crystal Structure and Related Properties of Manganese-Doped Barium Titanate Ceramics 607 Fig. .016. (c). Optical micrographs of the microstructure of BaTi1-xMnxO3 ceramics of both (a)–(e) as-fired and (f)–(j) H2-annealed samples with (a). (f) x 0. and (e). (b). Note different magnifications. (d).010.050. (i) 0. (g) 0. 2. (j) 0.005.
a hexagonal electron diffraction pattern of the grain in the center is shown. Bright-field TEM image (U 200 kV) of a thinned sample with a nominal composition of BaTi0. Grain sizes presented are roughly estimated values. respectively.95Mn0. Fig. Average grain size as a function of the nominal manganese content (x) of BaTi1-xMnxO3 before and after annealing under oxidizing and reducing conditions. a precise determination of the manganese content of the small grains by EPMA in compact specimens is hardly possible because of the rather large excitation volume of the X-rays. 3 Fig. EPMA-measured manganese concentration both integrally in a square and inside the grown grains as a function of the nominal manganese content of manganese-doped BaTiO3. But. 3. and the vertical and horizontal direction of the pattern image belong to the (001) and the (010) plane. especially in the case of platelike grains that are obtained by random cuts in the two-dimensional polished plane. some manganese . Electron beam coincides with the  direction.05O3 in the region of small globular grains. 83. 4. Vol. No. at least 5 mol% manganese seems to be soluble in the small globular grains of the manganese-rich samples with a bimodal microstructure. (B) Annealed Samples: Whereas the samples did not change their manganese content during annealing in air. 5. Contrary to the platelike grains. Fig.608 Journal of the American Ceramic Society—Langhammer et al. and a second with a Ti/Ba ratio of nearly two. indeed. Percentage values at the data symbols denote roughly estimated area portions of the different grain fractions. seem to occur—the first with a Ti/Ba ratio of nearly one. In the upper left-hand corner.
6. the d4 and the d9 configurations cause a stronger JTE compared to the others.March 2000 Crystal Structure and Related Properties of Manganese-Doped Barium Titanate Ceramics 609 Fig. which is in accordance with the experiments.. A 1. e. Looking at the microstructural development. Moreover.01.6 mol% manganese containing sample sintered at 1200°C for 1 h in air exhibits 86% t-BT compared to only 3 mol% at a sintering temperature of 1400°C. manganese. . Because the d1 electron configuration of Ti3 also causes a JTE.7 mol%). Illustration of the reciprocal shift of the adjacent Ba–O lattice planes A and C. for reduced h-BT as a liquid-phaseassisted one. which is explained as follows. We propose—at least in the case of manganese-doped BaTiO3—the influence of the Jahn– Teller distortion (see. IV. such as in the case of TiTi .02Ti0. 1). oxygen partial pressure.35 a definite excess of barium is necessary to incorporate a significant amount but. a sufficiently high density of oxygen vacancies is necessary to enable the microscopic steps of the transformation from the cubic to the hexagonal stacking of the Ba–O layers. Furthermore.) is necessary. of course. which is shown schematically in Fig. the sample tends to reach its equilibrium state by transformation of some h-BT into c/t-BT. which was shown in the case of B Ti ([TiTi ] 0. Probably because of the rather high effective ionic radii of Cu2 and Cu at 73 and 77 pm. respectively. this effect could be the driving force for the cubic 3 hexagonal phase transition in the case of undoped material as well. A similar relation also holds for divalent acceptors. this exaggerated grain growth is progressively hindered again. (2) Annealed Samples The partial restoration of the tetragonal phase of BaTiO3 (t-BT) during annealing in air can be understood easily if we assume that the results of the as-fired samples are not equilibrium values but frozen states.. The specimens annealed in a highly reducing atmosphere also exhibit a restoration of t-BT. Besides the necessary conditions. 14). the different effectivenesses of the dopants manganese.34 But concentrations on the order of 0.g.25 . it seems to be reasonable to assume that one common mechanism is responsible for the stability of h-BT. the high spin ground state was proved by ab initio calculations.015. causing the transformation from the cubic (ABCABC) to the hexagonal (ABACBC) stacking. By means of the known defect models of BaTiO3 (see. the ambient reducing atmosphere should originally favor a stabilization of the hexagonal phase and not vice versa. At a sufficiently high temperature. Ref.025. First. the concentration of Fe2 (d6) and Ni3 (d7). The transition from the cubic ABCABC to the hexagonal ABACBC stacking can be summarized as a reciprocal gliding of the adjacent lattice planes A and C. Consequently. d2. Thus. leading to hexagonal globular grains with a limited size. Refs. as in the case of decreased ambient oxygen activity.36 the real concentration of 2 CuTi is even smaller. is expelled from the specimens during annealing in a highly reducing atmosphere. is rather small at high temperatures in air as the ambient atmosphere.. are depicted. Two conditions must be accounted for by that mechanism. d7. 33) as such a driving force. Second.15 At manganese concentrations 0. e. On the other hand. two questions arise that cannot be answered easily. Refs. iron.3 mol% should 3 be sufficient. nickel. because their partial filling occurs in the higher sublevel.8 Of course. exhibiting a weak JTE. A third growth mechanism gradually dominates. 12. the well-known exaggerated grain growth of undoped BaTiO3 occurs. far from all of the copper ions at titanium sites. these two conditions can be fulfilled. Samples with a nominal composition of Ba1. annealing in a reducing (2) the incorporation of trivalent acceptor ions B at titanium sites also decreases the minimum temperature necessary to form h-BT in an analogous manner.3 mol%) by Wakamatsu and co-workers. the electron configuration exhibits the high-spin ground state because of weak crystal field splitting of the oxygen ions compared to the § In the case of manganese and chromium. e. the dependence of the percentage of t-BT on sintering temperature is shown. which is progressively hindered by the increasing manganese content. three different grain growth mechanisms occur that alternate continuously for increasing manganese content. According to the equation 2BaO B2O3 º 2BaBa 2BTi VO 5OO 3 spin-coupling energy.g. But. a second growth mechanism appears that results in large platelike grains of h-BT. their growth mechanism is of the same type that is described by Kolar et al. Only the layers BCA and BAC. because of the well-known valence change from Cu2 to Cu at 1000°C. (1)).14 –16 The pronounced anisotropic grain growth results from the surface energy anisotropy of the hexagonal polymorph. only the electron configurations d1. iron. d 4.30 The remaining manganese concentrations are measured by EPMA. A considerable amount of copper is a component of the secondary phase. during annealing at 1200°C (see Fig. The amount of manganese incorporated inside the grains is even somewhat lower than the integrally measured quantities because of manganese segregation in triple points. Discussion (1) As-Fired Samples Taking into account all previous work on the factors influencing the cubic/hexagonal phase transformation of BaTiO3 (temperature. In Table I. a minimum 3 concentration of BTi ions (B titanium. First. following the discussion above. probably because of the solubility limit of the manganese ions.02O3 and sintered at 1400°C for 1 h exhibit 31% hexagonal phase and a similar microstructure with large platelike grains similar to the case of manganese. 31.§ In this case. 8.11. at a fixed oxygen partial pressure. an increasing temperature causes both an increasing concentration of oxygen vacancies and an increasing concen3 tration of TiTi ions. Whereas the Mn3 (d 4) ions cause a complete transformation into h-BT at 1400°C for a rather small concentration of dopants (1. we also investigated the effect of copper because of the d9 configuration of Cu2 . 1 are related to mean values averaged over an area that covers various grains in the central region of the specimens. 3 . At low manganese concentrations of 0 x 0. a decrease of the oxygen partial pressure decreases the temperature for the necessary minimum concentration of both the oxygen vacancies and the trivalent titanium site ions (see Eq. d 6. the 3 concentration [TiTi ] even exceeds the concentration of the metal vacancies. and d 9 cause a Jahn–Teller effect (JTE) because of their partial filled sublevels. . Hence. 32) it can be easily derived that. For that reason. Obviously. Second. these results corroborate the high efficiency of the incorporation of Cu2 compared to the effect of iron and nickel. The corrected values shown in Fig. and nickel in stabilizing the hexagonal polymorph of BaTiO38 could be explained easily. respectively.98Cu0. Considering the BO6 complex (B 3d transition elements) in terms of the crystal field approach. 6. For x 0.g. concentration of some acceptor dopants) (see. the same explanation should be valid. it is necessary to add 10 mol% FeO or NiO to reach 50% h-BT at the same temperature. which is necessary for liquid-phase-assisted grain growth.12 With respect to all three factors mentioned above. the driving force for the phase transition must be elucidated. To prove this assumption with another electron configuration showing a strong JTE.
M.” J. “Effect of the Firing Atmosphere on the Cubic–Hexagonal Transition and the Chemical State of Titanium in Barium Titanate. Ceram.” J. 79. Ren.” Inorg. 1. H. “Effect of Oxidation States of Mn on the Phase Stability of Mn-Doped BaTiO3. “Exaggerated Growth of Hexagonal Barium Titanate ˘ under Reducing Sintering Conditions. “Structure Relations in Mixed Metal Oxides. 13 O. E. Ihrig.610 Journal of the American Ceramic Society—Langhammer et al. J. T. Columbus. Katz. The O2 ions that occupy the face-sharing planes of the TiO6 octahedra (Ti2O9 groups) of h-BT are more weakly bound because of their greater bonding length. Chem. Sci. Rase and R. Al-Allak.. pp.. E. 1015–18 (1996). the oxygen vacancies that are produced during annealing under reducing conditions are created preferentially at the lattice sites of the face-sharing planes. Subbarao. Ward. Michel-Calendini. and R.” Mater. OH.. B. N. Kyoto Institute of Technology. x Ts (°C) 0. The 1. Stephan Senz from the Max-Planck-Institut fur Mikrostrukturphysik ¨ Halle for the careful TEM and electron diffraction investigations. But. Mater. 60.” J. Pongratz. Recnik. 33. 24 S. Plenum. Ishida. Moretti and F. Chem. Huang.0 and 1. the cubic/ tetragonal structure reappears. (Yogyo Kyokaishi). “Effect of Manganese Addition on Phase Stability of Hexagonal BaTiO3. A. “Phase Equilibria in the System BaO–TiO2. 330 –37 (1948). Batllo. 19 F. Acknowledgment: atmosphere is much more efficient than annealing in air. Burn and G. The . 76. Two types of O2 ions exist that occupy different lattice sites with a slightly different bonding distance to the neighboring ions.35 Thus. decreases to 1. B. Shih. “An Investigation of the Cubic–Hexagonal Transition in Barium Titanate. Thus. 205–10 (1996). 23. Levinson. Sci. Lai. “Mn-Doped BaTiO3”.-C. Appl. 5 J. Roy. 38.050 Vol. 3263–71 (1988). “Compounds with the Hexagonal Barium Titanate Structure.-C. Mag. pp. Consequently. M.” Jpn.-H. Appl. T.-H.15 The surprising grain size reduction and the rearrangement of the grains during annealing in reducing atmosphere at 1200°C is not satisfactorily understood.. Sci. A possible explanation of this phenomenon could be as follows. Chen. As a driving force of the transformation from the cubic to the hexagonal crystal structure. 12 N. Y. Glaister and H. and S. Soc. Muller. Rev. Status Solidi A. 601–12 (1989). J. 166. 20. “On ¨ the Crystal and Defect Structure of Manganese-Doped Barium Titanate Ceramics. C. 1995. 113–18 (1990). Vol. Langhammer. Katz and R. and A.016 x 0.. 23 H. P.. abstract). G. 3.5 pm). Abicht. 3871–78 (1979)... 331–38 in Ceramic Microstructure: Control at the Atomic Level. Chen.” J. pp. J. Dickson. Jannot. “Dielectric and EPR Studies of Manganese-Doped Barium Titanate. 1181– 85 (1987). Kolar. 2088 –92 (1990). 74. Am. the activation energy for the creation of oxygen vacancies at those lattice sites is slightly lowered. and M. The crystal structure of h-BT is not as symmetric as the perovskite structure of c-BT.-M.5 pm) and MnTi (ri 64. Edited by L.-P. 83. Kay. and H. G. In our opinion. “The Origin and Growth Kinetics of Plate-Like ˘ Abnormal Grains in Liquid Phase Sintered Barium Titanate”. the drastically changed microstructure of samples with a nominal manganese content of 1. Soc. 1998. Matter. This mechanism is in competition 3 with the influence of the MnTi ions that should stabilize the hexagonal phase because of their Jahn–Teller distortion. “Mn-Doped Polycrystalline BaTiO3.” J. S. Maglione. Am.. The effective ionic radius (ri) of MnTi . Ward. Because we can assume that at 1200°C no liquid phase occurs.” Acta Crystallogr. and S. V. 3 4 which is somewhat 1 for TiTi (ri 60. for Several Manganese Concentrations. N. M. Electric Field. Wang and K. B: Condens. it is possible to explain the known experimental data of the phase transformation cubic 7 hexagonal. these explanations are hypothetical in nature and have to be proved by further investigations.7 mol% manganese. Jules. M. Weiss and G.. 67.” Phys. “The Crystal Structure of Hexagonal Barium Titanate. 43. 11 M. Desu and E. “Degradation of Mn-Doped BaTiO3 Ceramic under a ¨ High d. Mater. W.” Yogyo Kyokaishi (Engl. and K. Brinkmann. Desu and E. thus stabilizing the perovskite phase. 17 J. 51– 66 in Memoirs of the Faculty of Engineering and Design. 633 (1975). the high density of oxygen vacancies during annealing has to be responsible for these extensive solid-state grain-size-reduction and grain growth processes. Felgner. M. induced or stabilized by 3d transition elements qualitatively in a satisfying manner. Mater. 95. Ceram. 16 ˘ D. B. D. 36. Christian Eisenschmidt from the Department of Physics of the Martin-Luther-Universitat Halle for performing the quantitative XRD investiga¨ tions and Dr. 189 –206 in Advances in Ceramics. Manganese-doped BaTiO3 ceramics sintered at 1400°C in air change their room-temperature crystallographic structure from tetragonal to hexagonal between 0. Hagemann and H. Table I. “Impurity Energy Levels and Stability of Cr and Mn Ions in Cubic BaTiO3. 83. Am.c.020 0.. Ts (air). Niepce. “Addition of Ba2TiSi2O8 to Manganese-Doped Barium Titanate: Effect on Oxygen Diffusion and Grain-Boundary Composition. “Influence of Manganese on Lanthanum-Doped BaTiO3. 14 A.” Phys. Ceram. Duverger. U. a totally diffusion-controlled material transport mechanism has to be taken into account to describe that size reduction and total rearrangement of the grains. “Spontaneous Polarization Screening Effect and Trap-State Density at Grain Boundaries of Semiconducting Barium Titanate Ceramics.. the Goldschmidt tolerance factor. Summary The authors thank Dr. Mater. 10 D. Three different grain growth mechanisms control the microstructure in the whole doping range between 0 and 5 mol% manganese.. The microstructural development of samples annealed in reducing atmosphere exactly reflects the change of their phase composition related to the situation in the case of the as-sintered samples. 665– 68 (1981). 3 1000 1100 1200 1300 1400 92 90 86 84 3 88 88 85 74 0 74 69 43 12 0 explanation of the restoration of the cubic/tetragonal phase by annealing in a reducing atmosphere is more speculative and has to be checked by further investigations.-J. P. Kunaver. C.” J. 9 R. Phys. “High Resistivity BaTiO3 Ceramics Sintered in CO–CO2 Atmospheres. Soc. 109. S.-R. Soc.5 and 1. Therefore. Am. Ishida. “Extended Defects in Hexagonal BaTiO3.6 mol% is difficult to explain. Percentage of Tetragonal Phase of BaTi1 xMnxO3 Ceramics as a Function of the Sintering Temperature. F. Maher. Ishida.” J. “Valence Change and Phase Stability of 3d-Doped BaTiO3 Annealed in Oxygen and Hydrogen. L. Rev. which is 34 likely to be present in highly reducing conditions. 37. the influence of the Jahn–Teller distortion is proposed. 7 Y. A. Jpn. 6 D. No. Rodel and G. 280 – 86 (1991). 1412–16 (1994). 3522–27 (1987). Tomandl. C. Wu. Lo. Wakamatsu. B: Condensed Matter.” J.. Burbank and H. Polity. Phys.0 mol% can be explained by a third factor controlling the stability of crystal2 lographic phases. L.” Proc. Ceh. Evans Jr. and J. Wakamatsu. 3515–23 (1984). 21 J. One of them produces exaggerated platelike grains with hexagonal structure that corresponds to the analogous mechanism in undoped h-BT sintered in reducing atmosphere described by Kolar et al. Recnik and D. 14. 25 P. 8 R. 2453–58 (1979).. Phys. Takeuchi. Recnik. 106 –108 (1994). “Mechanistic Study of Reactions between Ceramics and Gases during Firing under Various Atmospheres”. 2 S. The total restoration of the tetragonal phase at manganese concentrations lower than 2. Lett. Takeuchi. New York. Illingsworth. and H.-C. 22 I. 102–13 (1955). American Ceramic Society. A. Of course. 3026 –29 (1961). 3 J. 205–11 (1964). This process destroys the Ti2O9 groups that make up two-thirds of the TiO6 octahedra of the hexagonal structure of BaTiO3.-C. Burn. “Exaggerated Anisotropic Grain Growth in ˘ Hexagonal Barium Titanate Ceramics.” Philos. Subbarao. Hence. Woods. Hence. the retransformed percentages of tetragonal phase decrease with increasing manganese content. 4 F. Sci. 102. 20 H. 15 D. Vol. G. 10. Skalicky.6 mol% manganese-containing sample even undergoes a nearly complete transformation from h-BT into c/t-BT. Ceram.” Ferroelectrics. Soc. 18 L. C. Kolar. H. Eibl.” J. References 1 I. “The Influence of Manganese on the Grain-Boundary Potential Barrier Characteristics of DonorDoped Barium Titanate Ceramics. K. 19. This hexagonal phase is a nonequilibrium one and can be partially retransformed into the cubic/tetragonal one by annealing both in air and in highly reducing atmosphere. Soc. Umeya. Rosenstein. T. amounts to 83 pm (high spin value).” Phys. A. Grain Boundary Phenomena in Electronic Ceramics. Schmelz. 763 (1960). 26. and M. Kolar.” Ferroelectrics. 219 –30 (1998).” J. 1981. Mineta. and M. 1. London.
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