Microstructural Characteristics of Strontium Magnesium Niobate

Microstructural studies were conducted on the domain boundaries in Sr(Mg_1/3Nb_2/3)O₃ (SMN) complex perovskite compound using X-ray diffractometry and transmission electron microscopy. Both the 1:2 chemical ordering of B-site cations and the tilting of oxygen octahedra were involved in SMN. SMN had a 1:2 ordered monoclinic unit cell, which was distorted by the antiphase tilting of oxygen octahedra. Two types of domain boundaries were found: the antiphase boundaries (APBs), which are not confined crystallographically, and the ferroelastic domain boundaries, which were parallel to the crystallographic planes. SMN had the superlattice reflections of type ±⅙[111] and ±½[111] in the electron diffraction patterns, which cannot be indexed in terms of the 1:2 ordered trigonal phase with only a hexagonal unit cell. The presence of the ferroelastic domains that contained both the 1:2 ordered and the antiphase tilting had been verified by a high-resolution transmission electron microscopy lattice image. The structure of SMN was well explained by a model proposed by other researchers. The formation of the 1:2 ordered domains preceded the ferroelastic domains. Normally, the growth of the ferroelastic domain is not affected by APBs, but it is interrupted by them when the driving force for growth is insufficient, resulting in the stoppage of the domains at APBs.     

Microstructure Characterization of the (1−x)La2/3TiO3·xLaAlO3 System

Microstructural characterizations on the (1− x )La_2/3TiO₃· x LaAlO₃ (LTLA) system were conducted using transmission electron microscopy. The presence of La₂Ti₂O₇ and La₄Ti₉O₂₄ phases in pure La_2/3TiO₃ is confirmed by the electron diffraction pattern. When x = 0.1, the ordering due to the A-site vacancies could be confirmed by the presence of antiphase boundaries (APBs) and return ½(100) superlattice reflection. As x increases, the ordering decreases and finally disappears when x = 0.6. The tilting of oxygen octahedra could be demonstrated by the presence of the ferroelastic domains in the matrix and return ½(111) and return ½(110) superlattice reflections in selected area electron diffraction patterns. In pure LaAlO₃, only the antiphase tilting of oxygen octahedra is present due to the presence of return ½(111) superlattice reflection. In the LTLA system of x = 0.1, both the antiphase and in-phase tiltings of the oxygen octahedra are involved; however, in the range of x from 0.3 to 0.9, the antiphase tilting of oxygen octahedra has appeared. The growth of the ferroelastic domains is influenced by the APBs in the matrix.     

Microstructure Characterizations in Calcium Magnesium Niobate

Microstructural studies on the domain boundaries in Ca(Mg_1/3CNb_2/3)O₃ (CMN) complex perovskite compound were conducted using X-ray diffractometry and transmission electron microscopy. The 1:2 chemical ordering of B-site cations and the tilting of oxygen octahedra were involved in the CMN microstructure, as inferred from the presence of two types of domain boundaries. One type was the antiphase boundaries (APBs), which did not lie on a specific set of crystallographic planes. These boundaries were caused by the chemical 1:2 ordering of B-site cations, magnesium and niobium. The other type was the ferroelastic domain boundaries, which were parallel to a certain crystallographic plane. Therefore, CMN had the 1:2 ordered monoclinic unit cell distorted by the antiphase or in-phase tilting of oxygen octahedra. CMN had the mixed phases rather than the homogeneous phase.     

Dielectric and Structural Characteristics in Barium Lanthanum Magnesium Niobate

The dielectric properties and their related microstructural characteristics in solid solutions of (1 — x )Ba(Mg_1/3Nb_2/3)O₃ (BMN)— x La(Mg_2/3Nb_1/3)O₃ (LMN) (BLMN) were investigated by measuring the relative permittivity (ɛ_r), Q value, and temperature coefficient of resonator frequency (τ_f), and by observing the microstructure using transmission electron microscopy. The trend of variation of the temperature coefficient of the dielectric permittivity (τ_ɛ) was the same for our solid solutions as that reported by Reaney et al . When the tolerance factor ( t ) was >1.01 in BLMN with composition x = 0 to 1.0, where the tilting of oxygen octahedra was not involved, the components of the microstructure included a disordered and transition phase as well 1:1 and 1:2 ordered phases. In the region where 1.01 < t < 0.96 with x = 0.2 to 0.7, the 1:1 order, the disorder, and the phase due to the antiphase tilting of oxygen octahedra were present. Finally, in the region where t < 0.96 with x = 0.7 to 1.0, the microstructure of BLMN was the same as that of the pure LMN, including the 1:1 order and the antiphase, inphase tilting of oxygen octahedra, and the antiparallel shift of A-site cations.     

Interfacial Structure of Disordered-Ordered Domain Boundaries in Lanthanum-Doped Barium Magnesium Niobate

Microstructural studies on the interfacial boundaries of disordered and 1:2 ordered domains in lanthanum-doped (Ba_0.975La_0.025)(Mg_0.34Nb_0.66)O₃ were performed using high-resolution transmission electron microscopy and synchrotron powder X-ray diffractometry. Disordered and 1:2 ordered domains both coexisted in a single grain. Each domain occupied its own region, and the interfaces were atomically sharp and coherent. The wavelength of the superlattice modulation in the 1:2 ordered domain was ∼0.71 nm. The transition from the 1:2 ordered region to the disordered one could be differentiated at the interface by using the superlattice modulations in the 1:2 ordered domain. From these observations, a deducible interfacial model also was presented.     

Microstructure and Dielectric Properties of Barium Strontium Magnesium Niobate

Dielectric properties and their related microstructural characteristics in solid solutions of (1 – x )Ba(Mg_1/3Nb_2/3)O₃– x Sr(Mg_1/3Nb_2/3)O₃ (BMN–SMN, or BSMN) were investigated by measuring the relative permittivity (ɛ_r), Q values, and temperature coefficient of resonator frequency (τ_f), and by observing microstructure using transmission electron microscopy. When the tolerance factor ( t ) was >0.99 in BSMN with composition 0 < x < 0.5, where the tilting of oxygen octahedra was not involved, the microstructure included only 1:2 ordered phase. In the region where 0.99 > t > 0.97 with 0.7 < x < 1.0, the phase due to the antiphase tilting of oxygen octahedral, the disordered phase, and the 1:2 ordered phase were also present. In a few of the grains, core–shell-type structures, whose main components were dislocations and stacking faults, were found in the solid solution of BSMN.     

Structural and Dielectric Characteristics of Barium Lanthanum Zinc Niobate

The dielectric properties and microstructural characteristics in solid solutions of Ba_{1− x} La _x [Zn_{(1+ x )/3}Nb_{(2− x )/3}]O₃ (BLZN) are investigated by measuring and observing these properties, respectively, by means of transmission electron microscopy and Raman spectroscopy. The 1:1 ordered structure of BLZN can be explained by the random-site model for the distribution of B-site cations. The decrease in the tolerance factor ( t ) by lanthanum substitution causes the tilting of oxygen octahedra. It appears that the onset of antiphase and inphase tilting causes the variation in the temperature coefficient of resonant frequency (τ_f). In the untilted region where t ≥1.01, the τ_f shows a linear increase with decreasing tolerance factor. The region of antiphase tilting, where 0.965≤ t <1.01, causes a rapid decrease in τ_f, including the reverse sign. The τ_f slowly increases, where t <0.965, which is due to the presence of inphase tilting of oxygen octahedra. The τ_f can be predicted by using the tolerance factor, and the near zero of τ_f can be obtained with lanthanum substitution in the solid solution of the BLZN system.     

Microstructure of Lanthanum Magnesium Niobate at Elevated Temperature

Microstructural studies of the complex perovskite compound La(Mg_2/3Nb_1/3)O₃ (LMN) were conducted using transmission electron microscopy (TEM) and X-ray diffractometry (XRD) at elevated temperatures. 1:1 chemical ordering of B-site cations and tilting of oxygen octahedra were observed in LMN. Three types of superlattice reflections, [1—2]{111}, [1—2]{110}, and [1—2]{100} were observed at room temperature and at 800°C in electron diffraction patterns. In the XRD experiments, the [1—2]{210} and [1—2]{300} extra peaks disappeared at temperatures >1200°C. However, the intensity of the superlattice [1—2]{111} peak did not change with increased temperature up to 1400°C. These results strongly indicated that the origin of superlattice reflection [1—2]{111} was different from that of the other superlattice reflections. It was mainly caused by the 1:1 chemical ordering of magnesium and niobium atoms. The TEM image observed at 800°C showed the ordered domain structures separated by the antiphase boundaries.     

Microstructure and Grain Boundary Structure of Na+-Diffused (Sr,Ca)TiO3 Capacitor-Varistor Ceramics

The microstructure of (Sr,Ca)TiO₃ capacitor-varistor materials has been investigated by employing electron microscopy techniques (TEM, STEM, HREM, EDX, and EPA). The material is found to contain (Sr,Ca)TiO₃ grains (∼30 μm) having perovskite crystal structure with domains, a Na⁺-diffused layer at the grain boundaries which is dependent on thermal diffusion conditions, and multiple-grain junctions in which the Ti _n O_2n–1 Magneli phase coexists with an amorphous intergranular phase. In addition, wider grain boundaries (10–30 nm), thin grain boundaries (∼1 nm), and clean grain boundaries which are free from intergranular phase were observed, and the effects of different grain boundaries on the diffusion of Na⁺are discussed.     

Interfacial Structure of Ordered Domains in Barium Lanthanum Magnesium Niobate

Microstructural studies on the interfacial boundaries of 1:1 and 1:2 ordered domains in (Ba_0.9La_0.1)(Mg_0.37Nb_0.63)O₃ were conducted using high-resolution transmission electron microscopy and X-ray diffractometry. Both 1:2 and 1:1 ordered domains coexisted in a fully ordered single grain. Each ordered domain occupied its own region, and the interfaces were atomically sharp and coherent. The wavelength of the superlattice modulation was ∼0.47 nm in the 1:1 ordered domain and ∼0.71 nm in the 1:2 ordered domain. The transition from the 1:2 ordered region to the 1:1 ordered region was clearly shown at the interface. These observations well support the structural models that have been previously presented.     

Domain Structures in Perovskite-Type Lanthanum Magnesium Titanate Ceramics

La(Mg_1/2Ti_1/2)O₃ ceramics were prepared using a conventional solid-state reaction route. X-ray diffraction analysis revealed that La(Mg_1/2Ti_1/2)O₃ possesses a distorted perovskite structure consisting of both in-phase and anti-phase tilting accompanied by anti-parallel shifting of La³⁺ cation. Superlattice reflections, indicative of 1:1-type ordering of Mg²⁺ and Ti⁴⁺ cations in the octahedral sites, were observed. The crystal symmetry was deduced to be monoclinic with P 2₁/ n space group (No. 14). Transmission electron microscopy analysis revealed two types of twin domains, classified according to the symmetry elements relating adjacent domains. Twin domains with specific orientations, related by mirror operations along {112} and (110) planes, were identified. La(Mg_1/2Ti_1/2)O₃ exhibited a high density of dislocations that interact with the twin boundaries resulting in incoherent twin interfaces. In addition, two morphologically distinct anti-phase domains were observed resulting from (i) off-center displacement of the La³⁺ cations, and (ii) 1:1 ordering of the B-site sublattice.     

Effect of Grain Boundary Structure on Diffusion-Induced Grain Boundary Migration in BaTiO3

The effect of grain boundary structure, either rough or faceted, on diffusion-induced grain boundary migration (DIGM) has been investigated in BaTiO₃. SrTiO₃ particles were scattered on the polished surfaces of two kinds of BaTiO₃ samples with faceted and rough boundaries and annealed in air for the samples with faceted boundaries and in H₂ for those with rough boundaries. In the BaTiO₃ samples with rough boundaries, an appreciable grain boundary migration occurred. In contrast, grain-boundary migration hardly occurred in the BaTiO₃ samples with faceted boundaries. The migration suppression observed in the sample with faceted boundaries was attributed to a low boundary mobility. The present experimental results show that DIGM is strongly affected by the boundary structure and can be suppressed by structural transition of boundaries from rough to faceted.     

Discontinuous Dissolution and Grain-Boundary Migration in Al2O3-Fe2O3 by Oxygen Partial Pressure Change

When sintered 95Al₂O₃-5Fe₂O₃ (wt%) specimens constituting corundum grains and iron aluminate spinel precipitates were annealed under high oxygen partial pressure (P_o2) where only a corundum phase is stable, fast dissolution of particulate spinel precipitates occurred, together with the migration of corundum grain boundaries. Behind the migrating boundaries, a corundum solid solution enriched with Fe₂O₃ formed. Discontinuous dissolution (DD) of particulate spinel precipitates thus occurred by P_o2 increase. In contrast, when 95Al₂O₃-5Fe₂O₃ specimens constituting only corundum grains were annealed under low P_o2 where both corundum and spinel phases are stable, grain boundaries migrated without spinel precipitation, leaving behind a corundum phase depleted of Fe₂O₃, similar to chemically induced grain-boundary migration (CIGM) observed during solute depletion. The volatilization of Fe₂O₃ appeared to cause the boundary migration without precipitation. The observed CIGM and DD would suggest various possibilities of microstructure control in other oxide systems through oxygen partial pressure change.     

Microstructural Observations in Barium Calcium Magnesium Niobate

Microstructural studies on (1 − x )Ba(Mg_1/3Nb_2/3)O₃– x Ca(Mg_1/3Nb_2/3)O₃ (BCMN) complex perovskite compounds, which are mixtures of Ba(Mg_1/3Nb_2/3)O₃ (BMN) and Ca(Mg_1/3Nb_2/3)O₃ (CMN), were conducted using scanning electron microscopy, transmission electron microscopy, and X-ray diffractometry. Pure BMN and CMN both have a 1:2 ordered structure, via the chemical ordering of B-site cations; however, the tilting of oxygen octahedra is involved in pure CMN, whose structure has a 1:2 ordered monoclinic unit cell that is characterized by (±1/6,±1/6,±1/6)-type superlattice reflections in electron diffraction patterns along the [110] zone axis that is based on a simple cubic perovskite. Studies of the morphologic differences have indicated two types of inhomogeneities in a mixture of the BCMN system: (i) a rather large-scale segregation (i.e., grain sizes of several micrometers), where the grains are separated compositionally as being barium-rich or calcium-rich, and (ii) fine-scale lamellar-type segregations 20 nm wide and 200 nm long. The segregation that is caused by Ba and Ca ions can be identified by the difference of superlattice modulations from high-resolution transmission electron microscopy lattice images.     

The {111} Growth Twins in Tetragonal Barium Titanate

The {1 1 1} twins frequently observed in pressureless-sintered BaTiO₃ ceramics have been analyzed by the X-ray diffractometry, scanning and transmission electron microscopy. Both the single twins and double lamellar twins are growth (or annealing) twins. The twins lying in the {1 1 1} mirror planes, which is not one of the symmetry elements of the (basic) crystal lattice's but that of the superlattice's, are therefore superlattice twins. The {1 1 1} twins, particularly the double twins, were found more frequently from samples sintered in an Ar atmosphere of lower oxygen partial pressure (pO₂). Further decreasing of pO₂ using the Ar-5% H₂ mixture has rendered the sintered samples entirely of hexagonal BaTiO₃, the 6H-polytype. The formation of such twins is attributed to changing of the corner-sharing TiO₆ octahedra to Ti₂O₉ face-sharing octahedra, which accommodates for local oxygen deficiency in tetragonal BaTiO₃. The stacking sequence alters accordingly from c-layer (constituting the 3C-polytype, treating tetragonal pseudo-cubic) to h-layer (as in (chc)₁(chc)₂ of 6H).     

Cation Ordering and Domain Boundaries in Ca[(Mg1/3Ta2/3)1−xTix]O3 Microwave Dielectric Ceramics

Cation ordering and domain boundaries in perovskite Ca[(Mg_1/3Ta_2/3)_{1− x} Ti _x ]O₃ ( x =0.1, 0.2, 0.3) microwave dielectric ceramics were investigated by high-resolution transmission electron microscopy (HRTEM) and Rietveld analysis. The variation of ordering structure with Ti substitution was revealed together with the formation mechanism of ordering domains. When x =0.1, the ceramics were composed of 1:2 and 1:1 ordered domains and a disordered matrix. The 1:2 cation ordering could still exist until x =0.2 but the 1:1 ordering disappeared. Neither 1:2 nor 1:1 cation ordering could exist at x =0.3. The space charge model was used to explain the cation ordering change from 1:2 to 1:1 and then to disorder. A comparison between the space charge model and random layer model was also conducted. HRTEM observations showed an antiphase boundary inclined to the (111) _c plane with a projected displacement vector in the 〈001〉 _c direction and ferroelastic domain boundaries parallel to the 〈100〉 _c direction.     

Imaging Secondary-Ion Mass Spectroscopy Observation of the Scavenging of Siliceous Film from 8-mol%-Yttria-Stabilized Zirconia by the Addition of Alumina

The scavenging of a resistive siliceous phase via the addition of Al₂O₃ was studied, using imaging secondary-ion mass spectroscopy (SIMS), given the improved grain-boundary conductivity in 8-mol%-yttria-stabilized zirconia (8YSZ). The grain-boundary resistivity in 8YSZ decreased noticeably with the addition of 1 mol% of Al₂O₃. Strong SiO₂ segregation at the grain boundaries was observed in a SIMS map of pure 8YSZ that contained 120 ppm of SiO₂ (by weight). The addition of 1 mol% of Al₂O₃ caused the SiO₂ to gather around the Al₂O₃ particles. The present observations provided direct and visual evidence of SiO₂ segregation at the grain boundaries (which had a deleterious effect on grain-boundary conductivity) and the scavenging of SiO₂ via Al₂O₃ addition.     

Singular Grain Boundaries in Alumina Doped with Silica

Pure Al₂O₃ powder compact sintered at 1400°C after adding 100 mol ppm of SiO₂ shows grain boundaries that are flat, even across the triple junctions. TEM observations show that these flat grain boundaries are parallel to the basal planes of the grains on one side. These flat grain boundaries must be singular. At such a low SiO₂ concentration and a low temperature, it is very unlikely that any liquid phase is present at these grain boundaries to cause such flat boundary shapes.     

Transformation-Induced Twinning: The 90° and 180° Ferroelectric Domains in Tetragonal Barium Titanate

Ferroelectric twin domains resulting from the cubic ( c ) to tetragonal ( t ) phase transformation at the Curie point T _C≈130°C in pressureless-sintered BaTiO₃ ceramics, using TiO₂-excess powder, have been investigated using scanning and transmission electron microscopy. Both 90° and 180° domains were identified by spot splitting along characteristic crystallographic directions in the selected-area diffraction patterns and/or from the shape of domain boundaries. Lamellar domains were found predominantly with the 90° types. The 180° domain boundaries mostly appeared wavy in shape, while the 90° ones, having sharpened ends, attained a dagger shape. Failure of Friedel's law in the non-centrosymmetric t -BaTiO₃ was adopted to validate the existence of the 180° domains. The 90° domains with boundaries lying in     are reflection–inversion twins, and the 180° domains lying in {100) _t and }220) _t are inversion twins. Convergent-beam electron diffraction was performed to ensure that changing of the polar direction [001] _t across the 90° and the 180° domain boundaries was consistent with the domain type. It was also used to confirm whether the 180°-type walls are inversion domain boundaries produced by the loss of an inversion center when the cubic phase transforms into tetragonal symmetry. The formation of such ferroelectric domains is discussed with reference to the crystal symmetry reduction from     ( c -phase) to P 4 mm ( t -phase) with a loss of mirror plane (m) and roto-inversion axis     upon c → t phase transformation.     

Silicon Nitride Based Ceramic Nanocomposites

Nanocomposites (Si₃N₄/SiC) were studied by combined high-resolution transmission electron microscopy and electron energy-loss spectroscopic imaging (ESI) techniques. In ESI micrographs three types of crystalline grains were distinguished: Si₃N₄ matrix grains (0.5 μΩ), nanosized SiC particles (<100 nm) embedded in the Si₃N₄, and large SiC particles (100–200 nm) at grain boundary regions (intergranular particles). Amorphous films were found both at Si₃N₄ grain boundaries and at phase boundaries between Si₃N₄ and SiC. The Si₃N₄ grain boundary film thickness varied from 1 to 2. 5 nm. Two kinds of embedded SiC particles were observed: type A has a special orientation with respect to the matrix, and type B possesses a random orientation with respect to the matrix. The surfaces of type B particles are completely covered by an amorphous phase. The existence of the amorphous film between the matrix and the particles of type A depends on the lattice mismatch across the interface. The mechanisms of nucleation and growth of Ω-Si₃N₄ grains are discussed on the basis of these experimental results.