Low-temperature sintering and microwave dielectric properties of MgTiO<Subscript>3</Subscript> ceramics

The effects of CuO–Bi₂O₃–V₂O₅ additions on the sintering temperature and the microwave dielectric properties of MgTiO₃ ceramics were investigated systematically. The CuO–Bi₂O₃–V₂O₅ (CuBiV) addition significantly lowered the densification temperature of MgTiO₃ ceramics from 1400 °C to about 900 °C, which is due to the formation of the liquid-phase of BiVO₄ and Cu₃(VO₄)₂ during sintering. The saturated dielectric constant (ε_r) increased, the maximum quality factor (Qf) values decreased and the temperature coefficient of resonant frequency (τ_f) shifted to a negative value with the increasing CuBiV content, which is mainly attributed to the increase of the second phase BiVO₄. MgTiO₃ ceramics with 6 wt.% CuBiV addition sintered at 900 °C for 2 h have the excellent microwave dielectric properties: ε _r= 18.1, Qf = 20300 GHz and τ_f = −57 ppm/ °C.     

Microwave dielectric properties and its compatibility with silver electrode of LiNb<Subscript>0.6</Subscript>Ti<Subscript>0.5</Subscript>O<Subscript>3</Subscript> with B<Subscript>2</Subscript>O<Subscript>3</Subscript> and CuO additions

The influences of B₂O₃ and CuO (BCu, B₂O₃: CuO = 1:1) additions on the sintering behavior and microwave dielectric properties of LiNb_0.6Ti_0.5O₃ (LNT) ceramics were investigated. LNT ceramics were prepared with conventional solid-state method and sintered at temperatures about 1,100 °C. The sintering temperature of LNT ceramics with BCu addition could be effectively reduced to 900 °C due to the liquid phase effects resulting from the additives. The addition of BCu does not induce much degradation in the microwave dielectric properties. Typically, the excellent microwave dielectric properties of ε_r = 66, Q × f = 6,210 GHz, and τ _f  = 25 ppm/^oC were obtained for the 2 wt% BCu-doped sample sintered at 900 °C. Chemical compatibility of silver electrodes and low-fired samples has also been investigated.     

Investigation on Electrical and Magnetic Properties of Gd-doped BiFeO<Subscript>3</Subscript>

Multiferroic ceramic samples of Bi_1−x Gd _x FeO₃ (x=0, 0.05, 0.1 and 0.15) have been prepared by rapid liquid-phase sintering technique. The effect of Gd substitution on ferroelectric and magnetic properties of Bi_1−x Gd _x FeO₃ ceramics has been investigated. The results of X-ray diffraction (XRD) patterns show that the single-phase BiFeO₃ sample has a rhombohedral structure and Gd³⁺ substitution for Bi³⁺ has not affected its structure. Experimental results suggest that for Bi_1−x Gd _x FeO₃ system, the ferroelectric and magnetic properties of BiFeO₃ are improved by Gd doping and the loop area increases with the Gd content. When x=0.15, saturated ferroelectric hysteresis loop is observed at room temperature with the maximal 2Pr=1.62 μC/cm², which is about 578.6% higher than that of BiFeO₃.     

Influence of Sm substitution on the phase,microstructure and microwave dielectric properties of SrLa<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>17</Subscript>

New dielectric ceramics in the SrLa_4−xSm_xTi₅O₁₇ (0 ≤ x ≤ 4) composition series were prepared through a solid state mixed oxide route to investigate the effect of Sm⁺³ substitution for La⁺³ on the phase, microstructure and microwave dielectric properties. At x = 0–3, all the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1500–1580 °C. At x = 4, a mixture of Sm₂Ti₂O₇ and SrTiO₃ formed. The maximum Sm⁺³-containing single phase ceramics, SrLaSm₃Ti₅O₁₇, exhibited relative permittivity (ε_r) = 42.6, temperature coefficient of resonant frequency (τ _f ) = −96 ppm/^oC and quality factor (Q _u f _o ) = 7332 GHz. An analysis of results presented here indicates that SrLa_4−xSm_xTi₅O₁₇ ceramics, exhibiting τ _f  ~ 0 and ε_r ~ 53 could be achieved at x ~ 1.4 but at the cost of decrease in Q _u f _o .     

Effect of lithium magnesium zinc borosilicate glass addition on densification temperature and dielectric properties of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> ceramics

Mg₂SiO₄ (Forsterite) ceramics were synthesized by solid state route. The effect of lithium magnesium zinc borosilicate (LMZBS) glass addition on the densification temperature and microwave dielectric properties of forsterite ceramics was investigated. The crystal structure and microstructure of ceramic–glass composites were studied by X-ray diffraction and scanning electron microscopic techniques. The dielectric properties of the sintered samples were measured in the microwave frequency range by the resonance method. Addition of 0.5 wt% LMZBS glass improved densification with ε _r = 7.3 and Qxf = 121,200 GHz. Addition of 15 wt% LMZBS glass lowered the sintering temperature to about 950 °C with ε _r = 6.75 and Qxf = 30,600 GHz. The reactivity of 15 wt% LMZBS glass added forsterite with silver was also studied. The result shows that forsterite doped with suitable amount of LMZBS glass is a possible material for LTCC and microwave substrate applications.     

Low-firing Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> microwave dielectric ceramics with BaCu(B<Subscript>2</Subscript>O<Subscript>5</Subscript>) additive

Phase purity, microstructure, sinterability and microwave dielectric properties of BaCu(B₂O₅)-added Li₂ZnTi₃O₈ ceramics and their cofireability with Ag electrode were investigated. A small amount of BaCu (B₂O₅) can effectively reduce the sintering temperature from 1075°C to 925°C, and it does not induce much degradation of the microwave dielectric properties. Microwave dielectric properties of ε _r = 23·1, Q × f = 22,732 GHz and τ _f = − 17·6 ppm/°C were obtained for Li₂ZnTi₃O₈ ceramic with 1·5 wt% BaCu(B₂O₅) sintered at 925°C for 4 h. The Li₂ZnTi₃O₈ +BCB ceramics can be compatible with Ag electrode, which makes it a promising microwave dielectric material for low-temperature co-fired ceramic technology application.     

Properties of neodymium-doped Ca<Subscript>0.15</Subscript>Sr<Subscript>1.85</Subscript>Bi<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>18</Subscript> ferroelectric ceramics

Bismuth-layered compound Ca_0.15Sr_1.85Bi_4−xNd_xTi₅O₁₈ (CSBNT, x = 0–0.25) ferroelectric ceramics samples were prepared by solid-state reaction method. The effects of Nd³⁺ doping on their ferroelectric and dielectric properties were investigated. The remnant polarization Pr of CSBNT ceramics increases at beginning then decreases with increasing of Nd³⁺ doping level, and a maximum Pr value of 9.6 μC/cm² at x = 0.05 was detected with a coercive field Ec = 80.2 kV/cm. Nd³⁺ dopant not only decreases the Curie temperature linearly, but also the dielectric constant (ε_r) and dielectric loss tangent (tan δ). The magnitudes of ε_r and tan δ at the frequency of 100 kHz are estimated to be 164 and 0.0083 at room temperature, respectively.     

Synthesis,microstructure and microwave dielectric properties of Ca<Subscript>4-x</Subscript>Mg<Subscript>x</Subscript>La<Subscript>2</Subscript>Ti<Subscript>5</Subscript>O<Subscript>17</Subscript> ceramics

Ca_4-xMg_xLa₂Ti₅O₁₇ ceramics were prepared by a solid state ceramic route for x = 0, 0.5, 1, 2, 3 and 4. The structure and microstructure of the ceramics were investigated using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. X-ray diffraction results show that the Ca_4-x Mg _x La₂Ti₅O₁₇ adopts an orthorhombic crystal structure with no secondary phase observed for x from 0 to 0.5. Secondary phase, MgTiO₃ occurs with further increasing doping level (1 ≤ x ≤ 3). When x = 4, mixture phases La_0.66TiO_2.993, MgTiO₃ and a trace of unknown phase coexist. Ca₄La₂Ti₅O₁₇ ceramic exhibits a relative permittivity (ε_r) ~ 65, quality factor (Q × f) ~13,338 GHz (at ~4.75 GHz), and temperature coefficient of resonant frequency (τ _f ) ~ 165 ppm/°C. The sintering temperature was distinctly reduced from 1,580 °C for x = 0 to 1,350 °C for x = 4. With increasing Mg content, ε_r and τ_f obviously decrease, while Q × f value initially decreases and then increases. The ceramic for x = 2 shows ε_r ~ 50, Q × f ~ 9,451 and τ _f  ~ 62.5 ppm/°C. By the complete replacement of Ca with Mg, Mg₄La₂Ti₅O₁₇ ceramic sintered at 1,350 °C for 4 h combines a high dielectric permittivity (ε _r  = 31), high quality factor (Q × f ~ 15,021) and near-zero temperature coefficient of resonant frequency (τ _f  ~ 4.0 ppm/°C). The materials are suitable for microwave applications.     

Phase formation, sintering behavior and microwave dielectric properties of bismuth and manganese co-doped [(Pb, Ca) La](Fe, Nb)O3+δ solid solution

The phase formation, sintering behavior and microwave dielectric properties of Bi₂O₃ and MnO₂ co-doped [(Pb, Ca) La](Fe, Nb)O_3+δ (PCLFN) ceramics were investigated. The Bi₂O₃ and MnO₂ binary dopants formed stable and low melting temperature solubilities at grain boundary which resulted in an effectively lowered sintering temperature by about 140 °C a more rapid sintering process and enhanced bulk densities. Sintering procedure has significant effect on grain size and porosities in ceramics. With high sintering temperature and time, the evaporation of PbO scaled up from surface toward the bulk and resulted in a Pb²⁺ deficient layer up to 0.25 mm depth under ceramic surface. Investigation of sintering dynamic revealed that either volume diffusion or second-order interface mechanism controlled the grain growth in present system. An optimal microwave dielectric properties of ε_r = 91.1, Q _f = 4,870 GHz and τ _f = 18.5 ppm/°C could be obtained in Bi₂O₃ and MnO₂ co-doped [(Pb, Ca) La](Fe, Nb)O_3+δ ceramics sintered at 1,050 °C for 4 h when the quality ratio of Bi₂O₃/MnO₂ was 1 and the doping content w = 1 wt%.     

Effect of ZnO on the microstructure and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> lead-free piezoelectric ceramics

K_0.5Na_0.5NbO₃–x ZnO (KNN–xZn) lead-free ceramics have been prepared using the conventional sintering technique and the effects of ZnO addition on the phase structure and piezoelectric properties of the ceramics have been studied. Our results reveal that a small amount of ZnO can improve the density of the ceramics effectively. Because of the high density and ZnO doping effects, the piezoelectric and dielectric properties of the ceramics are improved considerably. The good piezoelectric and dielectric properties of d ₃₃ = 114 pC/N, k _p = 0.36, ε _r = 395, and Q _m = 68 were obtained for the KNN ceramics doped with 1 mol% ZnO. Therefore, the KNN-1.0 mol%Zn ceramics is a good candidate for lead-free piezoelectric application.     

Low temperature sintering and microwave dielectric properties of Li<Subscript>3</Subscript>Mg<Subscript>2</Subscript>NbO<Subscript>6</Subscript> ceramics for LTCC application

The Li₃Mg₂NbO₆ ceramics doped with ZnO-B₂O₃-SiO₂ (ZBS) additives were synthesized via the conventional solid-state reaction process. The influence of ZBS additives on phase composition, sintering behavior, microstructure and microwave dielectric properties of Li₃Mg₂NbO₆ ceramics were investigated in detail. The XRD patterns showed that the sintered specimen presented a single phase and no secondary phase appeared. We found that proper amount of ZBS additives could significantly reduce the sintering temperature from 1250 to 925?°C and promote the densification of Li₃Mg₂NbO₆ ceramics. The ε_r and Q?×?f value were strongly affected by bulk density and grain size, respectively. As ZBS content increased, the τ_f value shifted toward negative direction. In summary, excellent microwave dielectric properties of ε_r?~?14.84, Q?×?f?~?73,987 GHz, τ_f?~??16.05 ppm/°C could be obtained in 0.5 wt.% ZBS modified sample when sintered at 925?°C for 4 h. Furthermore, the material was compatible with Ag electrode, demonstrating that it would be a promising candidate material for LTCC application.     

Structure,microwave dielectric and optical properties of Ln<Subscript>2/3</Subscript>Gd<Subscript>1/3</Subscript>TiNbO<Subscript>6</Subscript> (Ln=Ce,Pr, Nd and Sm) ceramics

The Ln_2/3Gd_1/3TiNbO₆ ceramic compositions are prepared through the solid state ceramic route. The compositions are calcined at 1250 °C and sintered in the range 1350–1435 °C. Structural analysis of the materials is done using X-ray diffraction analysis and vibrational spectroscopy. Surface morphology is examined by Scanning Electron Microscopy. Microwave dielectric properties such as dielectric constant (ε_r), quality factor (Q) and temperature coefficient of resonant frequency (T_f) are measured using cavity resonator method. The compositions have ε_r in between 46 and 41.8 and T_f in between +52 and +25 ppm/°C. By the substitution of Gd, the T_f is reduced considerably with a slight decrease in dielectric constant. Cerium based composition had additional reflections other than that of aeschynite structure. For Pr, Nd and Sm based systems, solid solutions were formed. UV visible spectrum of the representative composition is recorded and the band gap energy is estimated. Photoluminescence spectra of the samples are recorded and the transitions causing emissions are identified. The materials are suitable for microwave and optoelectronic applications.     

Microwave dielectric properties of Ba<Subscript>5</Subscript>Nb<Subscript>4</Subscript>O<Subscript>15</Subscript> ceramic by molten salt method

Ba₅Nb₄O₁₅ powders were synthesized by molten-salt method in NaCl–KCl flux at a low temperature of 650–900 °C for 2 h, which is lower than that of the conventional solid-state reaction. This simple process involved mixing of the raw materials and salts in a certain proportion. Subsequent calcination of the mixtures led to Ba₅Nb₄O₁₅ powders at 650–900 °C. XRD and SEM techniques were used to characterize the phase and morphology of the fabricated Ba₅Nb₄O₁₅ powders, respectively. After sintering at 1,300 °C for 2 h, the densified Ba₅Nb₄O₁₅ ceramics with good microwave dielectric properties of ε_r = 39.2, Q × f approximated as 27,200 GHz and τ _f  = 72 ppm/°C have been obtained.     

Effects of complex substitution of La and Nd for Bi on the microwave dielectric properties of BiNbO4 ceramics

La₂O₃ and Nd₂O₃ were used to substitute Bi₂O₃ and the effects of complex substitution on the sintering behavior and the microwave dielectric properties of BiNbO₄ ceramics were studied. With 0.5 wt.% CuO-V₂O₅ mixtures addition, all of the Bi_1−x(La_0.38Nd_0.62)_xNbO₄ ceramics could be densified below 920 °C. The triclinic phases are identified in Bi_1−x(La_0.38Nd_0.62)_xNbO₄ ceramics with x=0.01 sintered at 820 °C and the triclinic intensities increase with increasing the x value and sintering temperature. The saturated bulk density slightly decreases from 7.17 to 7.13 g/cm³ and the ε_r value from 44.24 to 42.76 with increasing x from 0 to 0.07 for Bi_1−x(La_0.38Nd_0.62)_xNbO₄ ceramics. The saturated Q×f value is between 10,300 and 12,400 GHz depending on the x value. The τ_f values of dense Bi_1−x(La_0.38Nd_0.62)_xNbO₄ ceramics decrease from 28.32 to 12.79 ppm/°C with x varying from 0 to 0.01 and remain almost unchanged with further increasing x.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Influence of Zr doping on the dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

Pure and Zr-substituted CaCu₃(Ti_1−x Zr _x )₄O₁₂ (x = 0, 0.01, 0.02, 0.03) ceramics were prepared by the Pechini method. X-ray powder diffraction analysis indicated the formation of single-phase compound, and all the diffraction peaks were completely indexed by the body-centered cubic perovskite-related structure. The effects of Zr⁴⁺ ion substituting partially Ti⁴⁺ ion on the dielectric properties were investigated in frequency range between 100 Hz and 1 GHz. The low frequency (f ≤ 10⁵ Hz) dielectric constant decreases with Zr substitution and the high frequency (f ≥ 10⁷ Hz) dielectric constant is unchanged. Interestingly, a low-frequency relaxation was observed at room temperature through Zr substitution. The observed dielectric properties in Zr-substituted samples were discussed using the internal barrier layer capacitor model. A corresponding equivalent circuit was adopted to explain the dielectric dispersion. The characteristic frequency of low-frequency relaxation rises due to the decrease of the resistivity of grain boundary with Zr substitution, which is likely responsible for the large low-frequency response at room temperature.     

Microwave dielectric properties of 3Li2O–Nb2O5–3TiO2 ceramics with Li2O–V2O5 additions

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 3:1:3 has been investigated. The compound is composed of two phases, the Li₂TiO₃ and “M-phase” solid solution phase. The microwave dielectric ceramic has low sintering temperature (∼1100 °C) and good microwave dielectric properties of a relatively high permittivity (∼51), high Q × f value up to 8700, and small temperature coefficient (∼37 ppm/°C). The low-amount doping of 0.83Li₂O–0.17V₂O₅ (LV) can effectively lower the sintering temperature from 1100 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 1 wt.% LV-doped ceramic sintered at 900 °C has better microwave dielectric properties of ε_r = 51.3, Q × f = 7235 GHz, τ _f  = 22 ppm/°C, which suggests that the ceramics can be applied in microwave LTCC devices.     

Synthesis of MgTiO<Subscript>3</Subscript> by solid state reaction and characteristics with addition

Magnesium titanate was synthesized by the solid state reaction. Powder XRD method was used to identify the phases and content, which indicates that pure phase of MgTiO₃ can be synthesized by the solid state reaction even without the addition of excess MgO. Doped with 5 at.% CaTiO₃ and 6 wt.% ZnNb₂O₆, MgTiO₃ ceramics sintered at 1300 °C possess excellent microwave dielectric properties: a dielectric constant ε_r of 21, a τ _f value of 0 ppm/°Cand a Q × f value of 130,000 GHz (at 13 GHz).     

Sol–gel synthesis, densification, and electrical properties of CuO–B2O3 doped Ba6?3xR8+2xTi18O54 (R?=?Nd) microwave dielectric ceramics

The low-temperature confirmable Ba_6−3x R_8+2x Ti₁₈O₅₄ (BNT, R = Nd, x = 2/3) ceramics were prepared by means of a citrate sol–gel soft-chemical method and the addition of sintering aid. Nano-sized BNT crystallite powders (~80 nm) were successfully synthesized as indicated by transmission electron microscopy and X-ray diffractometry. The powder compacts exhibit enhanced sintering activity and can be well densified at 925 °C with the aid of a small amount of CuO and B₂O₃. Compared to pure BNT ceramics prepared by a solid-state reaction method, not only was the sintering temperature significantly decreased, but also the good microwave dielectric properties of dielectric constant ε_r = 63 and quality factor Q × f = 5200 GHz were maintained. Moreover, the relationship between the microstructure, densification, and electrical properties was discussed.     

Effects of LiF addition on the sintering behavior and microwave dielectric properties of Li<Subscript>2</Subscript>Mg<Subscript>3</Subscript>SnO<Subscript>6</Subscript> ceramics

Li₂Mg₃SnO₆ (abbreviation for LMS) ceramics doped with 1–4 wt% lithium fluoride (LiF) were prepared by the conventional solid-state reaction method. The effects of LiF addition on the phase compositions, sintering behaviors and microwave dielectric properties of LMS ceramics were investigated. A small amount of LiF addition could effectively decrease the sintering temperatures due to the liquid phase in the sintering process and induced no apparent degradation of the microwave dielectric properties. The optimized quality factor values for each composition firstly increased and then decreased with the increase of the LiF content. Whereas, the optimized dielectric permittivity increased with increasing of the LiF content. Distinguished microwave dielectric properties with a dielectric constant (ε _r) of 11.13, a quality factor (Q·f) of 104,750 GHz, and a temperature coefficient of resonant frequency (τ _f ) of ?10.83 ppm/°C were obtained for LMS ceramics sintered at 950?°C doped with 3 wt% LiF, which showed that the materials were suitable for the low temperature co-fired ceramics applications (LTCC).