Effect of Orientation on the Ferroelectric Behavior of (Pb,Sr)TiO3 Thin Films

Pb_0.6Sr_0.4TiO₃ (PST) ferroelectric thin films were prepared on two different substrates by sol–gel methods. Films derived on the LaNiO(LNO)/Pt/Ti/SiO₂/Si substrates showed a strong (100) preferred orientation. The PST thin films grown on the LNO/Pt/Ti/SiO₂/Si(100) substrate showed a non-uniform rounded grain size distribution and have a larger polarization and lower coercive field E _c. The dependence of electrical properties derived on the Pt/Ti/SiO₂/Si and LNO/Pt/Ti/SiO₂/Si substrates has been studied, with a focus on the change of dielectric constant versus direct current (DC) bias field. The dielectric and ferroelectric properties of the Pb_0.6Sr_0.4TiO₃ thin films deposition on two kinds of substrates were investigated as a function of temperature, frequency and DC bias field.     

Low-Temperature Sintering of (Ba0.6Sr0.4)TiO3

An addition of just 0.4 wt% Li₂O to (Ba_0.6Sr_0.4)TiO₃ powder was able to reduce the sintering temperature to ≤900°C and produce ceramics with a relative density of 97%. Small amounts of two secondary phases were formed during this process: Li₂TiO₃ and Ba₂TiO₄. The addition of Li₂O depresses the ferroelectric character of the (Ba_0.6Sr_0.4)TiO₃ and, as a result, reduces the permittivity, improves the temperature coefficient of permittivity, and reduces the dielectric losses. The tunability shows no significant variation with Li₂O concentration and remains between 16.5% and 13.5%. A low-temperature sintering mechanism was proposed. The mechanism involves the intermediate formation of BaCO₃, its melting and the incorporation of Li⁺ into the BST. The sintering mechanism can be characterized as reactive liquid-phase sintering.     

Effect of Sintering Aids on Microstructures and PTCR Characteristics of (Sr0.2Ba0.8)TiO3 Ceramics

The effects of liquid-phase sintering aids on the microstructures and PTCR characteristics of (Sr_0.2Ba_0.8)TiO₃ materials have been studied. The grain size of sintered materials monotonically decreases with increasing content of Al₂O₃–SiO₂–TiO₂ (AST). The ultimate PTCR properties with ρ_ht/ρ_rt as great as 10^5.61 are obtained for fine-grain (10-μm) samples, which contain 12.5 mol% AST and were sintered at 1350°C for 1.5 h. The quantity of liquid phase formed due to eutectic reaction between AST and (Sr,Ba)TiO₃ is presumably the prime factor in determining the grain size of samples. The grains grow rapidly at the sintering temperature in the first stage until the liquid phase residing at the grain boundaries reaches certain critical thickness such that the liquid–solid interfacial energy dominates the mechanism of grain growth.     

Influence of SiO2 Addition on the Dielectric Properties and Microstructure of (Ba0.96Ca0.04)(Ti0.85Zr0.15)O3 Ceramics

In this study, the effect of SiO₂ doping on the sintering behavior, microstructure, and dielectric properties of BaTiO₃-based ceramics was investigated. Silica was added to (Ba_0.96Ca_0.04)(Ti_0.85Zr_0.15)O₃ (BCTZ) powder prepared using the solid-state method. SiO₂-doped BCTZ ceramics with a high density and a uniform grain size were obtained and sintered at 1220°C in a reducing atmosphere. A second phase (BaTiSiO₅) existed in samples when SiO₂ was added in excess of 1%. The amount of the second phases was observed to increase as the number of SiO₂ additives increased. It was found that BCTZ ceramics sintered with SiO₂ are helpful in reducing the sintering temperature for a typical thick film and MLCC applications. However, there were disadvantageous effects on the dielectric properties with mere addition of SiO₂ addition (3% and 5%) due to higher formation of BaTiSiO₅. Doping with a small amount of silica can improve the sintering and dielectric properties of BCTZ ceramics. In addition, to understand the effect of the BaTiSiO₅ phase on the dielectric properties of BCTZ ceramics, the BaTiSiO₅ composition was synthesized from individual BaCO₃, TiO₂, and SiO₂ powders using conventional solid-state methods. X-ray diffraction results show the presence of mainly the crystalline phase, BaTiSiO₅, in the sintered ceramics.     

Co-Additions of TiO2 and SiO2 Crystalline Fillers to Tailor the Properties of BaO–ZnO–B2O3–SiO2 Glass for Application to Barrier Ribs of Plasma Display Panels

The influence of co-additions of crystalline TiO₂ and SiO₂ fillers (10 wt% addition in total) to BaO–ZnO–B₂O₃–SiO₂ glass on resultant properties was investigated from the viewpoint of applying the material to the barrier ribs of plasma display panels. The substitution of SiO₂ for TiO₂ reduced the dielectric constant significantly, while it maintained high optical reflectance and appropriate coefficient of thermal expansion (CTE) in the case when TiO₂ alone was used. A 5–7.5 wt% SiO₂ addition with 2.5–5 wt% TiO₂ under the constraint of 10 wt% total fillers demonstrated an optical reflectance of about 55%, a CTE of about 8.3 × 10⁻⁶ K⁻¹ (compatible with glass panels), and a dielectric constant of about 7.5, which are promising properties for the barrier rib application.     

Effect of SiC on Interfacial Reaction and Sintering Mechanism of TiB2

Compacts of TiB₂ with densities approaching 100% are difficult to obtain using pressureless sintering. The addition of SiC was very effective in improving the sinterability of TiB₂. The oxygen content of the raw TiB₂ powder used in this research was 1.5 wt%. X-ray photoelectron spectroscopy showed that the powder surface consisted mainly of TiO₂ and B₂O₃. Using vacuum sintering at 1700°C under 13–0.013 Pa, TiB₂ samples containing 2.5 wt% SiC achieved 96% of their theoretical density, and a density of 99% was achieved by HIPing. TEM observations revealed that SiC reacts to form an amorphous phase. TEM-EELS analysis indicated that the amorphous phase includes Si, O, and Ti, and X-ray diffraction showed the reaction to be TiO₂+ SiC → SiO₂+ TiC. Therefore, the improved sinterability of TiB₂ resulted from the SiO₂ liquid phase that was formed during sintering when the raw TiB₂ powder had 1.5 wt% oxygen.     

A Novel Temperature-Compensated Microwave Dielectric (1−x)(Mg0.95Ni0.05)TiO3−xCa0.6La0.8/3TiO3 Ceramics System

The microstructure and microwave dielectric properties of a (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics system have been investigated. The system was prepared using a conventional solid-state ceramic route. In order to produce a temperature-stable material, Ca_0.6La_0.8/3TiO₃ was added for a near-zero temperature coefficient (τ_f). With partial replacement of Mg²⁺ by Ni²⁺, the dielectric properties of the (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature and the composition. An excellent Q × f value of 118,000 GHz can be obtained for the system with x =0.9 at 1325°C. For practical application, a dielectric constant (ɛ_r) of 24.61, a Q × f value of 102,000 GHz, and a temperature coefficient of resonant frequency (τ_f) of −3.6 ppm/°C for 0.85(Mg_0.95Ni_0.05)TiO₃−0.15Ca_0.6La_0.8/3TiO₃ at 1325°C are proposed. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

Degradation of Bioactive Polydimethylsiloxane–CaO–SiO2–TiO2 and Poly(tetramethylene oxide)–CaO–TiO2 Hybrids in a Simulated Body Fluid

It has been shown that polydimethylsiloxane (PDMS)–CaO–SiO₂–TiO₂ and poly(tetramethylene oxide) (PTMO)–CaO–TiO₂ hybrids form apatite on their surfaces in a simulated body fluid (SBF) and show mechanical properties similar to those of human cancellous bones. In the present study, changes, caused by soaking in SBF, were measured in the mechanical properties of PDMS–CaO–SiO₂–TiO₂ hybrids with different CaO and TiO₂ contents and PTMO–CaO–TiO₂ hybrids with different CaO contents. Significant decreases in the strength and strain at failure of the hybrids were observed for the PDMS–CaO–SiO₂–TiO₂ hybrids with high CaO or TiO₂ contents and PTMO–CaO–TiO₂ hybrids with a high CaO content after soaking in SBF for 4 w. This indicates that incorporation of a large amount of CaO component into the hybrids should result in the deterioration of the hybrids in the body environment.     

Preparation of TiO2 Nanoparticles on Different SiO2 Supports by the Adsorption Phase Technique

The influence of supports on the preparation of TiO₂ nanoparticles by the adsorption phase technique is studied in detailed. Series temperature experiments of two types of supports (named as SiO₂ A and B) were used. Energy-dispersive analysis by X-ray indicates that the concentration of TiO₂ on both supports decreases with temperature increasing. TiO₂ quantity on SiO₂ A decreases sharply between 40° and 60°C, whereas the temperature range for SiO₂ B is between 30° and 50°C. X-ray diffraction (XRD) shows that grain size of TiO₂ particles on two SiO₂ surfaces is all below 7 nm. It is also shown by XRD that particles on SiO₂ A decrease sharply as in the quantity curve of TiO₂, but particles on SiO₂ B all change gradually and TiO₂ particles on SiO₂ B are more uniform in transmission electron spectroscopy. The similarly of both supports is considered to be the reason for the similar changes in Ti concentration, and the different characteristics of the internal/external surface lead to variant quantity and grain size, as well as characteristics of TiO₂.     

Microwave Dielectrics in the (La1/2Na1/2)TiO3–Ca(Fe1/2Nb1/2)O3 System

Dielectric properties of the system (1 − x)(La_1/2Na_1/2)TiO₃– _x Ca(Fe_1/2Nb_1/2)O₃, where 0.4 # x # 0.6, have been investigated at microwave frequencies. The temperature coefficient of resonant frequency (τ_f), nearly 0 ppm/°C, was realized at x = 0.58. These ceramics had perovskite structure and showed relatively low dielectric losses. A new dielectric material applicable to microwave devices having Q · f of 12000–14000 GHz and a dielectric constant (ε_r) of 59–60 has been obtained at 1300–1350°C for 5–15 h sintering.     

Immiscibility Area in the System TiO2–ZrO2–SiO2

A furnace for use in conjunction with the X-ray spectrometer was developed which was capable of heating small powdered specimens in air to temperatures as high as 1850°C. This furnace was also used for the heating and quenching of specimens in air from temperatures as high as 1850°C. An area of two liquids coexisting between 20 and 93 weight % TiO₂ above 1765°± 10°C. was found to exist in the system TiO₂–SiO₂, which is in substantial agreement with the previous work of other investigators. The area of immiscibility in the system TiO₂–SiO₂ was found to extend well into the system TiO₂–ZrO₂–SiO₂. The two liquids were found to coexist over a major portion of the TiO₂ (rutile) primary-phase area with TiO₂ (rutile) being the primary crystal beneath both liquids. The temperature of two-liquid formation in the ternary was found to fall about 80°C. with the first additions of ZrO₂ up to 3%. With larger amounts of ZrO₂ the change in the temperature of the boundary of the two-liquid area was so slight as to be within the limits of error of the temperature measurement. Primary-phase fields for TiO₂ (rutile), tetragonal ZrO₂, and ZrTiO₄ were found to exist in the system TiO₂–ZrO₂–SiO₂. SiO₂ as high cristobalite is known to exist in the system TiO₂–ZrO₂–SiO₂.     

Nanostructure of TiO2 Nano-Coated SiO2 Particles

We characterized SiO₂–TiO₂ nano-hybrid particles, prepared using the sol–gel method, using high-resolution transmission microscopy. A few nanometer-ordered TiO₂ anatase crystallites could be observed on the monodispersed SiO₂ nanoparticle surface. The quantum size effect of the TiO₂ anatase crystallites is attributed to the blue shift of the absorption band. The rough surface of the SiO₂–TiO₂ nano-hybrid particles was derived from the developed growth planes of the TiO₂ anatase crystallites, grown from fully hydrolyzed Ti alkoxide that did not react with acetic acid during the crystallization process at 600°C thermal annealing.     

Role of Liquid Phase in PTCR Characteristics of (Ba0.7Sr0.3)TiO3 Ceramics

The role of liquid phase in the enhancement of the PTCR (positive temperature coefficient of resistance) effect in (Ba_0.7Sr_0.3)TiO₃ (BST) with the addition of AST (4Al₂O₃· 9SiO₂· 3TiO₂) is investigated in this paper. The AST–BST samples were characterized with optical microscopy, transmission electron microscopy, energy-dispersive spectroscopy, and impedance spectroscopy. Microscopic observations showed that slower cooling might facilitate the precipitation of the (Ba,Sr)TiO₃ phase from the liquid phase on matrix grains since the amount of liquid phase was reduced with a decreasing cooling rate. Impedance spectroscopy indicated that this variation accompanied the change in the intrinsic properties of grain boundaries, which could not be explained by well-known oxidation effects. With the aid of a brick-layer model and high-resolution transmission electron microscopy (HRTEM), it appeared that the change in electrical characteristics of grain boundaries with decreasing cooling rate originated from the precipitation of (Ba,Sr)TiO₃. Finally, the effect of precipitated (Ba,Sr)TiO₃ on the PTCR characteristics is discussed in terms of the acceptor-state density and the polarization state at grain boundaries.     

Formation and Sintering of TiO2 (Anatase) Solid Solution in the System TiO2-SiO2

In the TiO₂-SiO₂ system, anatase solid solutions (ss) containing up to similar/congruent ∼15 mol% SiO₂ are formed in the as-prepared state by the hydrazine method. The lattice parameters a and c decrease linearly from 0.3785 to 0.3776 nm and from 0.9514 to 0.9494 nm, respectively, with increased SiO₂ content. At high temperatures, the solid solutions by transformation decompose into rutile and amorphous SiO₂. The anatase(ss) powders have been characterized for particle size and surface area. They consist of very fine particles (7-25 nm). Surface areas at low temperatures are very high and do not drop below 60 m²/g at 1000°C. Nanostructured anatase(ss) ceramics, with greaterthan/equal to 99.5% of theoretical density and an average grain size of 72 nm, have been fabricated by hot isostatic pressing for 1 h at 850°C and 196 MPa. Their mechanical and electrical properties have been examined.     

Compound Formation and Phase Equilibria in the System PbO-SiO2

Compound formation in the system PbO-SiO₂ was studied; the results are contrasted with those previously reported. Fifteen binary phases, 4 of which had not been reported, were prepared in the present study. The new phases include Pb₅Si₈O₂₁, an orthorhombic polymorph of PbSiO₃, Pb₃SiO₅, and a high-SiO₂ phase containing ∼ 60 mol% SiO₂. It was shown that Pb₃SiO₅ is thermodynamically stable relative to Pb₂SiO₄ and 4PbO.SiO₂ below 640±5°C. A revised phase equilibrium diagram is presented.     

Sintering and Electrical Properties of Titania- and Zirconia-Containing ln2O3-Sno2(ITO) Ceramics

The deposition rate and film quality of In₂O₃-SnO₂ (ITO) transparent electrodes processed by sputtering are improved when using dense sputtering targets. Unfortunately, ITO ceramics do not sinter easily. It is shown that addition of TiO₂ (<1 wt%) to ITO greatly increases densification without degrading electrical properties of sputtered films. The influence of ZrO₂ and SiO₂ was also investigated.     

Sintering and Crystallization of CaO–Al2O3–ZrO2–SiO2 Glasses Containing Different Amount of Al2O3

In this work several complementary techniques have been employed to carefully characterize the sintering and crystallization behavior of CaO–Al₂O₃–ZrO₂–SiO₂ glass powder compacts after different heat treatments. The research started from a new base glass 33.69 CaO–1.00 Al₂O₃–7.68 ZrO₂–55.43SiO₂ (mol%) to which 5 and 10 mol% Al₂O₃ were added. The glasses with higher amounts of alumina sintered at higher temperatures (953°C [lower amount] vs. 987°C [higher amount]). A combination of the linear shrinkage and viscosity data allowed to easily find the viscosity values corresponding to the beginning and the end of the sintering process. Anorthite and wollastonite crystals formed in the sintered samples, especially at lower temperatures. At higher temperatures, a new crystalline phase containing ZrO₂ (2CaO·4SiO₂·ZrO₂) appeared in all studied specimens.     

Liquid–Solid Equilibria in the System NiO–TiO2–SiO2 in the Temperature Range 1430° to 1660°C

Equilibrium relations in the system NiO–TiO₂–SiO₂ in air have been investigated in the temperature range 1430° to 1660°C. The most conspicuous feature of the phase relations is the existence of a cation-excess spinel-type phase, in addition to NiO and NiTiO₃, on the liquidus surface and at subsolidus temperatures down to 1430°C. Three invariant points have been located on the liquidus. There is a peritectic at 1540°C characterized by coexisting NiO ( ss ), spinel( ss ), cristobalite, and liquid of composition 47 wt% NiO, 29 wt% TiO₂, and 24 wt% SiO₂. Two eutectics are present, one at 1480°C, with spinel( ss ), NiTiO₃, cristobalite, and liquid (42 wt% NiO, 43 wt% TiO₂, and 15 wt% SiO₂), as the coexisting phases. The other is at 1490°C with NiTiO₃, rutile, cristobalite, and liquid (32 wt% NiO, 56 wt% TiO₂, and 12 wt% SiO₂). A liquid miscibility gap extends across the diagram from the two bounding binary systems NiO–SiO₂ and TiO₂–SiO₂.     

Single Crystals of (PbxSr1-x) TiO3 Grown by Traveling Heater Method

A procedure is presented for growing single crystals of (Pb_xSr_1-x)TiO₃ by passing solvent zones through poly-crystalline rods of the same composition (THM). The solvent zone composition for homogeneous solid solution growth was chosen from the pseudoquaternary system 2PbO: 1B₂O₃-2SrO:1B₂O₃-PbTiO₃-SrTiO₃. Crystals with compositions throughout the complete range of PbTiO₃-SrTiOs solid solutions were grown. Emphasis was placed on crystal compositions near (Pb_0.25Sr_0.78) TiO₃ which have Curie temperatures just below room temperature. The dielectric constants, Curie temperatures, and optical properties of these single crystals are presented. Nonlinear dielectric and electrooptic behaviors are also demonstrated.     

A Study of the Phase Relations of ZrO2–TiO2 and ZrO2–TiO2–SiO2

The phase relations of the systems ZrO₂–TiO₂ and ZrO₂–TiO₂–SiO₂ were investigated. X-ray diffraction techniques served as the principal means of analysis. The binary system ZrO₂–TiO₂ was found to be one of partial solid solutions with no intermediate compounds. A eutectic point was found to exist at 50 to 55 weight % ZrO₂ and 1600°C. A preliminary investigation of the ternary system ZrO₂–TiO₂–SiO₂, although not extensive, resulted in a better understanding of this system, with a fairly accurate location of some of its boundary lines. A eutectic point was located at 2% ZrO₂, 10% TiO₂, and 88% SiO₂ at approximately 1500°C.