Low-temperature sintering and microwave dielectric properties of Ba<Subscript>2</Subscript>Ti<Subscript>3</Subscript>Nb<Subscript>4</Subscript>O<Subscript>18</Subscript> ceramics

The effects of CuO and H3BO3 additions on the low-temperature sintering,microstructure,and microwave dielectric properties of Ba2Ti3Nb4O18 ceramics were investigated.The addition of less amount of CuO (< 1 wt%) considerably facilitated the densification of Ba2Ti3Nb4O18 ceramics.Appropriate addition of H3BO3 (< 3.5 wt%) remarkably improved the microwave dielectric properties of ceramics.The addition of H3BO3 and CuO successfully reduced the sintering temperature of Ba2Ti3Nb4O18 ceramics from 1300 to 1050 ℃.B...     

Effect of ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass addition on the microwave dielectric properties of BaO-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The effect of ZnO-B₂O₃(ZB) glass addition on the sintering behavior, microstructures and microwave dielectric properties of BaO-Nd₂O₃-TiO₂-Bi₂O₃ (BNTB) system was investigated with the aid of X-ray diffraction, scanning electron microscopy and capacitance meter. It is found that the ZB glass addition, acting as a sintering aid, can effectively lower the sintering temperature of BNTB system to 850 °C. The dielectric constant of BNTB-ZB ceramics increases with the increase of soaking time and the value of dielectric loss decreased with increasing soak time. The optical dielectric properties at 1 GHz of ɛ=74, tan δ=4×10⁻⁴, and TCC=25 ppm/°c were obtained for the BNTB system doped with 25 wt% ZB glass sintered at 850 °C for 2 h, representing that the BNTB-ZB ceramics could be promising for multilayer low temperature co-fired ceramics applications.     

Effect of La doping on microstructure and ferroelectric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by sol-gel method

The Bi4Ti3Oi2 and Bi3.25La0.75Ti3O12 thin films were prepared on the Pt/Ti/SiO2/Si substrate using the sol-gel method. The effect of La doping on the microstructure and ferroelectric properties of Bi4Ti3O12 films were investigated. Both the Bi4Ti3O12 and Bi3.25La0.75Ti3O12 thin films exhibited typical bismuth layered perovskite structure. The 2Pr （remanent polarization） value of Bi3.25La0.75Ti3O12 thin films is 18.6 μC/cm^2, which is much larger than that of Bi4Ti3O12 thin films. And the Bi3.2eLa0.75Ti3O12 films show fatigue-free behavior, while the Bi4Ti3O12 thin films exhibit the fatigue problem. The mechanism of improvement of La doping was discussed.     

Preparation and ferroelectric properties of Bi<Subscript>3.4</Subscript>Ce<Subscript>0.6</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films grown by sol-gel method

We have investigated the preparation and properties of Bi_3.4Ce_0.6Ti₃O₁₂ thin films. The Bi_3.4Ce_0.6Ti₃O₁₂ thin films were fabricated on the Pt/Ti/SiO₂/Si substrates using sol-gel method. The structure and morphology of the films were characterized using X-ray diffraction and atomic force microscopy. The thin films showed a perovskite phase and dense microstructure. The dielectric constant and the dissipation factor of the Bi_3.4Ce_0.6Ti₃O₁₂ thin films were about 172 and 0.031 at 1 kHz, respectively. The 2P _r and 2E _c of the Bi_3.4Ce_0.6Ti₃O₁₂ thin films were 67.1 μC/cm² and 299.7 kV/cm, respectively, under an applied field of 600 kV/cm. The Bi_3.4Ce_0.6Ti₃O₁₂ film did not show fatigue up to 4.46×10⁹ switching cycles at a frequency of 1 MHz, and showed good insulating behavior according to the test of leakage current. Supported by the Natural Science Foundation of Hubei Province (Grants No. 2004ABA082)     

Orientation of Bi<Subscript>3.2</Subscript>La<Subscript>0.8</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films with different annealing schedules

Fatigue-free Bi_3.2La_0.8Ti₃O₁₂ ferroelectric thin films were successfully prepared on p-Si (100) substrates using metalorganic solution deposition process. The orientation and formation of 5-layers thin films were studied under different processing conditions using XRD. Experimental results indicate that increase in annealing time at 700 °C after preannealing for 10 min at 400 °C can remarkably increase (200)-orientation of the films derived from the precursor solutions with two contents of citric acid. Meanwhile, high content of citric acid increases the film thickness and is conducive to the a-orientation of the films with the preannealing, and low concentration of the solution is conducive to the c-orientation of the films without the preannealing.     

Enhanced Ferroelectric Polarization in Laser-ablated Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Thin Films by Controlling Preferred Orientation

Polycrystalline Bi₄Ti₃O₁₂ thin films with various fractions of a-axis, c-axis and random orientations have been grown on Pt(111)/Ti/SiO₂/Si substrates by laser-ablation under different kinetic growth conditions. The relationship between the structure and ferroelectric property of the films was investigated, so as to explore the possibility of enhancing ferroelectric polarization by controlling the preferred orientation. The structural characterization indicated that the large growth rate and high oxygen background pressure were both favorable for the growth of non-c-axis oriented grains in the Bi₄Ti₃O₁₂ thin films. The films with high fractions of a-axis and random orientations, i e, f (a-sxis) = 28.3% and f (random) = 69.6%, could be obtained at the deposition temperature of 973 K, oxygen partial pressure of 15 Pa and laser fluence of 4.6 J/cm², respectively. It was also noted that the variation of ferroelectric polarization was in accordance with the evolution non-c-axis orientation. A large value of remanent polarization (2Pr = 35.5 μC/cm²) was obtained for the Bi₄Ti₃O₁₂ thin films with significant non-c-axis orientation, even higher than that of rare-earth-doped Bi₄Ti₃O₁₂ films.     

Phase structure and electrical properties of La<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped BiInO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> ceramics with high curie temperature

The phase structure and electrical properties of pure and La2O3-doped Bi-InO3-PbTiO3 （BI-PT） ceramics were studied respectively. In （1 -x）BI-xPT （x=0.72-0.80） ceramics, the stability of tetragonal phase increased with increasing x, and pure perovskite structure was obtained for x=-0.80 ceramics. The phase transition temperature range was between 575 ℃ and 600 ℃ for x=0.72-0.80 ceramics, higher than that of PT （-490 ℃）. The c/a ratio almost linearly decreased with increasing La2O3 content in x-0.80 ceramics. It is believed that Pb^2＋ vacancies were formed by La^3＋ substituting Pb^2＋ in La2O3-doped BI-PT ceramics. Tc shifted to lower temperature by 30 ℃/mol% La2O3. The maximum dielectric constant 8557 around 559 ℃ was exhibited in 0.5mol%-doped BI-0.80PT ceramics. La2O3-doped ceramics could be poled resulting from decreasing of c/a ratio and improving of dielectric loss and resistivity. The maximum piezoelectric coefficient d33 was 12 pC/N for 2mol%-doped BI-0.80PT ceramics.     

Structure and dielectric properties of ZnO and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> doped BaO-TiO<Subscript>2</Subscript> system microwave ceramics

The microwave dielectric properties and microstructure of BaTi4.3ZnyO9.6＋y ＋0.02 mol% SnO2＋0.01 mol% MnCO3＋x mol% Nb2O5（x=0-0.05, y=0-0.08） system ceramics were studied as a function of the amount of ZnO and Nb2O5 doped. Addition of （y=0-0.05） ZnO and （x=0-0.025） Nb2O5 enhanced the reactivity and decreased the sintering temperature effectively. It also increased the dielectric constant ε r and quality factor Q（=1/tan 8） of the system due to the substitution of Ti^4＋ ions with incorporating Zn^2＋and Nb^5＋ ions, which was analyzed by the reaction ZnO＋Nb2O5＋ 3 TiTxTi →ZnTi＋ 2NbTi＋3TiO2. When the system doped with （y=0.05） ZnO and （x=0.025） Nb205 were sintered at 1 160 ℃ for 6 h, the εr. Qf0 value and rfwere 36.5, 42 000 GHz, and＋1.8 ppm/℃, respectively, at 5 GHz.     

Dielectric tunable properties of BaTi<Subscript>4</Subscript>O<Subscript>9</Subscript>-doped Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> microwave composite ceramics

BaTi₄O₉-doped Ba_0.6Sr_0.4TiO₃ (BST) composite ceramics were prepared by the conventional solid-state reaction and their structure, dielectric nonlinear characteristics and microwave dielectric properties were investigated. The secondary phase of the orthorhombic structure Ba₄Ti₁₃O₃₀ is formed among BST composite ceramics with the increase of BaTi₄O₉. At the same time, a duplex or bimodal grains size distribution shows fine grains in a coarse grain matrix. The degree of frequency dispersion of dielectric permittivity below T _m is increased initially and then decreased with respect to BaTi₄O₉. As the BaTi₄O₉ content increases, the tunability of composite ceramics decreases, while the Q value increases. Interestingly, 70 wt% BaTi₄O₉-doped BST has a tunability ∼4.0% (under 30 kV/cm biasing) versus a permittivity ∼68 and quality factor ∼134.1 (at ∼3.2 GHz). Supported by the Ministry of Science and Technology of China through 973-project (Grant No. 2009CB623302), the Cultivation Fund of the Key Scientific and Technical Innovation Project, Ministry of Education of China (Grant No.707024), Shanghai Committee of Science and Technology (Grant No. 07DZ22302), and Shanghai Foundation Project under 06JC14070     

Preparation and properties of crystallizable Glass/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composites for LTCC material

The investigated low temperature Co fired ceramics(LTCC) composite of 60wt% CaO-Al2O3-B2O3-SiO2 glass and 40wt% α-Al2O3 as a filler is a non-reactive system, which is a critical part of the low temperature Co fired ceramics process. Through a study on densification process, the phase transformation and microstructure can be revealed. Its composites typically consist of CaO-Al2O3-B2O3-SiO2 glass and α-Al2O3 powders of average particle size (D50=3.49 mm). The sintering behavior, phase evaluation, sintered morphology, and microwave dielectric properties were investigated. In the fire range of 800 to 900 ℃, the composites were crystallized after completion of densification. It is found that the composites start to densify at 825 ℃, simultaneously, the dielectric constant (εr) reaches its maximum. With increasing heat-treatment temperatures, due to the loose microstructure of the material, tanδ increases slightly. The last of the sintered samples were identified as partly Anorthite at 850 ℃. At that temperature it has εr of 7.9 and tanδ less than 1×10-3, and can be used as a promising LTCC material.     

Structure and Electric Properties of （1-x）（Bi1/2Na1/2） TiO3-xBaTiO3 Systems

The structural, dielectric and piezoelectric properties of （1-x）（Bi1/2Na1/2） TiO3-xBaTiO3 ceramics were investigated for the compositional range, x=0.02, 0.04, 0.06, 0.08, 0.10. The samples were synthesized by a conventional solid-state reaction technique. All compositions show a single perovskite structure, and X-ray powder diffraction patterns can be indexed using a rhombohedral structure. Lattice constants and lattice distortion increase while the amount of BaTiO3 increases. The X-ray diffraction results show the morphotropic phase boundary （MPB） of （1-x）（Bi1/2Na12） TiO3-xBaTiO3 exists in near x=0.06-0.08. Temperature dependence of dielectric constant eT33/ε0 measurement reveals that all compositions experience one structural phase and two ferroelectric phases transition below 400℃： rhombohedral （or rhombohedral plus tetragonal） ferroelectric phase ←→ tetragonal antiferroelectric phase ←→ tetragonal paraelectric phase. Relaxor behaviors exist in the course of ferroelectric to antiferroelectric phase transition. Dielectric and piezoelectric properties are enhanced in the MPB range for （ 1-x）（Bi1/2Na1/2）TiO3-xBaTiO3.     

Ferroelectric properties of Bi<Subscript>4</Subscript>Zr<Subscript>0.5</Subscript>Ti<Subscript>2.5</Subscript>O<Subscript>12</Subscript> thin films prepared on LaNiO<Subscript>3</Subscript> bottom electrode by sol-gel method

The Bi4Zr0.5Ti2.5O12 (BZT) thin films were fabricated on the LaNiO3 bottom electrode using sol-gel method. The structure and morphology of the films were characterized using X-ray diffraction, AFM and SEM. The results show that the films have a perovskite phase and dense microstructure. The 2Pr and 2Vc of the Pt/BZT/LaNiO3 capacitor are 28.2 μC/cm2 and 14.7 V respectively at an applied voltage of 25 V. After the switching of 1×1010 cycles, the Pr value decreases to 87% of its pre-fatigue values. The dielectric constant (ε) and the dissipation factor (tanδ) of the BZT thin films are about 204 and 0.029 at 1 kHz, respectively. The films show good insulating behavior according to the test of leakage current. The clockwise C-V hysteresis curve observed shows that the Pt/BZT/LaNiO3 structure has a memory effect because of the BZT film's ferroelectric polarization.     

Effect of Constituent Core-sizes on Microstructure and Dielectric Properties of BaTiO<Subscript>3</Subscript>@(0.6Ba-TiO<Subscript>3</Subscript>-0.4BiAlO<Subscript>3</Subscript>) Core-Shell Material

The fundamental characteristics of varied initial core-sizes of BaTiO₃(BT) and its influential role on the morphology and dielectric properties of BaTiO₃@0.6BaTiO₃-0.4BiAlO₃(BT@0.6BT-0.4BA) ceramic samples were studied. Alkoxide sol-precipitation method was adopted as revised chemical route to synthesize the constituent “core” BT powders in a dispersed phase, whereas the distinctive initial nano-sized particles were affected by the pre-calcination temperatures (600-900 °C).The microstructure of the uncoated BT ceramics revealed an exaggerated grain growth with an optimized dielectric constant (ε_max >9 000) whilst the coated ceramics behaved otherwise (grain growth inhibited) when sintered at an elevated temperature. Regardless of the previously studied solubility limit (about 0.1%) of BT-BA samples, BT@0.6BT-0.4BA maintained a maximum dielectric constant (ε_max) ranging from 1 592 to 1 708 and tan δ less than 2% under a unit mole ratio at room temperature. In view of all these analyses, the initial nanometer sizes of the as-prepared BT-core powders combined with the increase effect of cation substitutions of Bi³⁺ and Al³⁺ in the shell content, induced the diffuse transition phase of BT@0.6BT-0.4BA composition.     

Preparation and piezoelectric properties of CuO-added (Ag<Subscript>0.75</Subscript>Li<Subscript>0.1</Subscript>Na<Subscript>0.1</Subscript>K<Subscript>0.05</Subscript>)NbO<Subscript>3</Subscript> lead-free ceramics

CuO-doped (Ag_0.75Li_0.1Na_0.1K_0.05)NbO₃ (ALNKN-xCuO, x = 0–2mol%) lead-free piezoelectric ceramics were prepared by the solid-state reaction method in air atmosphere. The effects of CuO addition on the phase structure, microstructure, and piezoelectric properties of the ceramics were investigated. The experimental results show that the ALNKN ceramics without doping CuO possess rhombohedral phase along with K2Nb6O16-type phase and metallic silver phase. For all of the CuO-doped ALNKN ceramics, a pure perovskite structure with the orthorhombic phase was obtained by enclosing the samples in a corundum tube. A homogeneous microstructure with the grain size of about 1 μm was formed for the ceramics with 0.5mol% CuO. The grain size increases with increasing amount of CuO. The temperature dependence of dielectric properties indicates that the ferroelectric phase of the ALNKN-xCuO ceramics becomes less stable with the addition of CuO. The ceramics with x = 1mol% exhibit relatively good electrical properties along with a high Curie temperature. These results will provide a helpful guidance to preparing other AN-based ceramics by solid-state reaction method in air atmosphere.     

Enhanced Low-field Magnetoresistence in the Absence of Mn Content in Polycrystalline La0.67Ca0.33MnO3

Magnetic and electrical transport properties of the La0.67Ca0.33Mn1-xO3 （x=0-0.16）, which were prepared by the sol-gel method followed by sintering treatment at 1 450, 1 100 and 900 ℃, respectively, were investigated. Experimental results show that, with the increase of x, the resistivity of samples increases and the insulator-metal transition temperature shifts towards lower temperature. Meanwhile, the intrinsic megnetoresistance effect is weakened and the extrinsic magnetoresistance is enhanced. For the samples with x=0.16 and 0.10 sintered at 1 100 ℃ and 900 ℃, respectively, low field magnetoresistance as high as about 50% can be observed. Furthermore, for the samples sintered at 1 100 ℃ and 900 ℃, the grain size is not only controlled by about sintering temperature, but also by the absence of Mn content x.     

Microwave sintering of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript>-WC-Co cermets

Composite powders of nanocrystalline WC-10Co (15wt%),Y2O3 (8mol%) stabilized nanocrystalline ZrO2 (30wt%),industrial cobalt powder (4.5wt%) and submicron Al2O3 (55wt%) composite powders were fabricated by high-energy ball-milling process.The nanocomposite powders were consolidated by microwave sintering process at temperature ranged 1300℃-1550℃ for 15min,respectively.The optimum consolidation conditions,such as temperature,were researched during microwave sintering process.Vickers Hardness of the consolidated cermets was measured by using a Vickers indentation test,and density of specimens was also determined by Archimedes’ principle.Microwave sintering process could not only increase the density of Al2O3-ZrO2-WC-Co cermets and reduce the porosity,but also inhibit abnormal grain growth.     

Investigation on phase evolution of the ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass ceramics

ZnO-B₂O₃-SiO₂-Al₂O₃-Na₂O glass doped with nucleating agent TiO₂ was prepared with melting-quenching method and the effect of nucleating agent on the crystallization behavior and phase evolution of this glass was investigated by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The experimental results show that the glass transition temperature and the first crystallization temperature decrease from 630 °C and 765 °C to 595 °C and 740 °C, respectively, with introduction of TiO₂ into glass. There is no diffraction peaks in the XRD pattern but it is no longer transparent for the base glass without nucleating agent after heat treatment, which suggests the serious phase separation occurred, and the observation by SEM indicates that the phase separation is developed by nucleation and growth mechanism. However, there are two different crystals ZnAl₂O₄ and NaAlSiO₄ present in the glass containing TiO₂ after heat treating at 575 °C for 2 h and 740 °C for 6 h, respectively. What is interesting is that NaAlSiO₄ disappears as the crystallization time at 740 °C increases from 6 h to 12 h, and more ZnAl₂O₄ crystal is formed, namely, the further formation of ZnAl₂O₄ is at cost of NaAlSiO₄ with increasing crystallization time. And observation of the morphology of glass ceramics shows great difference with increasing crystallization time. Moreover, the ability of ZnO-B₂O₃-SiO₂-Al₂O₃-Na₂O glass ceramics against attacking of 1M HCl solution is increased by the crystals precipitated in heat treatment process.     

Dielectric Properties of B2O3 Doped MgTiO3-CaTiO3 System Ceramics

The dielectric ceramics with a main crystal phase of MGTiO3 and additional crystal phase of CaTiO3 were prepared by the conventional electronic ceramics technology .the strucures of MgTiO3 are ilmenitetype,and belong to hexagonal syngony.the ratio of MgTiO3 to Ca TiO3 doping on the dielectric properties of MGTiO3-CaTiO3(MCT)ceranics were inrestigated.the addition of B2O3 decreases the sintering temperatnre and results in rapid desification without obrious negative effect on the Q values of the system(Q=1/tan ).B2O3 exists as liquid phase in the sintering process,promoting the reactions as a singering agent.     

Microstructures and fatigue-free properties of the La<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by modified sol-gel technique

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) and Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were fabricated on Pt/TiO₂/SiO₂/Si (100) substrates by a modified sol-gel technique. X-ray diffraction indicated that these films were of single phase with random polycrystalline orientations. The surface morphologies of the films were observed by scanning electron microscope, showing uniform, dense films with grain size of 50–100 nm. Well-saturated hysteresis loops of the films were obtained in metal-ferroelectric-metal type capacitors with Cu top electrodes at an applied voltage of 400 kV/cm, giving the remanent polarization (2P _r) and coercive field (2E _c) values of the films of 25.1 μC/cm² and 203 kV/cm for BLT, and 44.2 μC/cm² and 296 kV/cm for BNT, respectively. Moreover, these capacitors did not show fatigue behaviors after up to 1.75×10¹⁰ switching cycles at the test frequency of 1 MHz, suggesting a fatigue-free character. The influences of the La³⁺ and Nd³⁺ doping on the properties of the films were comparatively discussed. Supported by the National Key Basic Research and Development Program of China (Grant No. 2006CB932305) and the Natural Science Foundation of Hubei Province, China (Grant No. 2004ABA082)     

Effect of aluminum addition on microstructure and properties of SiO<Subscript>2</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO vitrified bond

Influence of aluminum addition on the structures and properties of SiO₂-B₂O₃-Al₂O₃-CaO vitrified bond at low sintering temperature and high strength was discussed. FTIR and XRD analyses were used to characterize the structures of the basic vitrified bond with different contents of aluminum. The bending strength and the thermal expansion coefficients were also tested. Meanwhile, the microstructures of composite specimens at sintering temperature of 660 °C were observed by scanning electron microscope (SEM). The experimental results showed that the properties of vitrified bond with 1wt% aluminum were improved significantly, where the bending strength, Rockwell hardness, and thermal expansion coefficient of the vitrified bond reached 132 MPa, 63 HRB, and 6.73×10^-6 °C^-1, respectively.