Normal sintering of (K, Na)NbO3-based lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics have received more attention due to the environmental protection of the earth. (K, Na)NbO₃-based ceramics are one of the most promising candidates. Normal sintering of un-doped and Li/Ta co-doped (K, Na)NbO₃ ceramics was investigated to clarify the optimal sintering condition for densification, microstructure and electrical properties. It was found that density increased greatly within a narrow temperature range but turned to decrease when the sintering temperature slightly exceeded the optimal one. Piezoelectric properties also showed similar relationship between the density and sintering temperature, but the highest piezoelectric strain coefficients were obtained at the temperatures lower than that for the highest density. The grain growth and property change as a function of sintering temperature were discussed on basis of the formation of liquid-phase and the composition deviation caused by the volatilization of alkali components during sintering.     

Effects of mechanical activation and two-step sintering on the structure and electrical properties of cordierite-based ceramics

The mechanical activation can help reduce production costs and modify cordierite-based materials. In this study, the structure and electrical properties of the mechanically activated MgO-Al₂O₃-SiO₂ system have been analyzed. The mixtures of MgO-Al₂O₃-SiO₂ powders were mechanically activated in a planetary ball mill for time periods ranging from 0 to 160 min. Structural investigations were performed on the obtained powders. The effects of activation and a two-step sintering process on the microstructure and crystal structure were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The thermal stability was analyzed using DTA. Electrical measurements showed variations of the dielectric constant (ε_r) and loss tangent (tan δ) as a function of the time of mechanical treatment.     

Sintering behavior and microwave dielectric properties of Bi2O3–ZnO–Nb2O5-based ceramics sintered under air and N2 atmosphere

The sintering behavior and dielectric properties of the monoclinic zirconolite-like structure compound Bi₂(Zn_1/3Nb_2/3)₂O₇ (BZN) and Bi₂(Zn_1/3Nb_2/3−xV_x)₂O₇ (BZNV, x = 0.001) sintered under air and N₂ atmosphere were investigated. The pure phase were obtained between 810 and 990 °C both for BZN and BZNV ceramics. The substitution of V₂O₅ and N₂ atmosphere accelerated the densification of ceramics slightly. The influences on microwave dielectric properties from different atmosphere were discussed in this work. The best microwave properties of BZN ceramics were obtained at 900 °C under N₂ atmosphere with _r = 76.1, Q = 850 and Q_f = 3260 GHz while the best properties of BZNV ceramics were got at 930 °C under air atmosphere with _r = 76.7, Q = 890 and Q_f = 3580 GHz. The temperature coefficient of resonant frequency τ_f was not obviously influenced by the different atmospheres. For BZN ceramics the τ_f was −79.8 ppm/°C while τ_f is −87.5 ppm/°C for BZNV ceramics.     

Microwave dielectric properties and co-firing with copper of (Bi1−xCux)(Nb1−xWx)O4 ceramics

Effect of substitution of CuO and WO₃ on the microwave dielectric properties of BiNbO₄ ceramics and the co-firing between ceramics and copper electrode were investigated. The (Bi_1−xCu_x)(Nb_1−xW_x)O₄ (x = 0.005, 0.01, 0.015, 0.02) composition can be densified between 900 and 990 °C. The microwave dielectric constants lie between 36 and 45 and the pores in ceramics were found to be the main influence. The Q values changes between 1400 and 2900 with different x values and sintering temperatures while Q_f values lie between 6000 and 16,000 GHz. The microwave dielectric losses, mainly affected by the grain size, pores, and the secondary phase, are discussed. The (Bi_1−xCu_x)(Nb_1−xW_x)O₄ ceramics and copper electrode was co-fired under N₂ atmosphere at 850 °C and the EDS analysis showed no reaction between the dielectrics and copper electrodes. This result presented the (Bi_1−xCu_x)(Nb_1−xW_x)O₄ dielectric materials to be good candidates for LTCC applications with copper electrode.     

Processing of Bi1.5ZnNb1.5O7 ceramics for LTCC applications: Comparison of synthesis and sintering methods

Bismuth zinc niobate posses a cubic pyrochlore structure and normally is obtained by the conventional solid-state reaction. The great disadvantage of this method is the lack of chemical homogeneity, requiring high synthesis and sintering temperatures (higher than 1000 °C), which is an impeditive for BZN application in LTCC with silver as the internal electrode. The aim of this paper is to compare, from synthesis to sintering, BZN ceramics, derived either from chemically or conventionally synthesized powders, sintered either in both conventional oven for 2 h or microwave oven for 15 min. The results showed that chemically synthesized BZN ceramics sintered in microwave oven at 900 °C for 15 min presented a relative density of 97%, while those obtained by conventional method required 1000 °C to reach the same density. Despite the short period for thermal treatment in microwave oven, the electrical properties of BZN ceramics are compatible with those sintered in conventional oven for 2 h.     

Preparation and microwave dielectric properties of low-loss MgZrNb2O8 ceramics

A novel low-loss microwave dielectric material MgZrNb₂O₈ was reported for the first time. Single-phase MgZrNb₂O₈ was prepared by a conventional mixed-oxide route and sintered in the temperature range of 1280–1360 °C. The microstructure and microwave dielectric properties were investigated systematically. The X-ray diffraction results showed that all samples exhibit a single wolframite structure. When the sintering temperature was lower than 1340 °C, the Q×f value mainly depended on the relative density. However, when the sintering temperature was above 1340 °C, the Q×f value mainly relied on the grain morphology in addition to the density. The MgZrNb₂O₈ ceramic sintered at 1340 °C for 4 h exhibited excellent microwave dielectric of ε_r=26, Q×f=120,816 GHz (where f=6.85 GHz), and τ_f=?50.2 ppm/°C. These results demonstrate that MgZrNb₂O₈ could be a promising candidate material for the application of highly selective microwave ceramic resonators and filters.     

Low temperature sintering of CCTO using P2O5 as a sintering aid

Recent work on CCTO is directed towards decreasing its dissipation factor and further raising its dielectric constant by using different dopants. Also attempts have been made to lower its sintering temperature by adding different sintering aids so as to save energy and use low-cost electrodes (Ag–Pd or base metal) for making multilayer capacitors. Normally, CCTO needs a processing temperature of 1100 °C and above for densification. We report the formation of dense CCTO ceramics at a temperature as low as 1000 °C by adding P₂O₅ as a sintering aid. The samples showed dielectric constant value as high as 40,000, though the dissipation factor values remained high like those reported for pure CCTO.     

Effect of the excess of bismuth on the morphology and properties of the BaBi2Nb2O9 thin films

In this study, the effect of bismuth content on the crystal structure, morphology and electric properties of barium bismuth niobate (BaBi₂Nb₂O₉) thin films was explored with the aid of X-ray diffraction (XRD), scanning electron microcopy (SEM), atomic force microscopy (AFM) and dielectric properties. BaBi₂Nb₂O₉ (BBN) thin films have been successfully prepared by the polymeric precursor methods and deposited by spin coating on Pt/Ti/SiO₂/Si (1 0 0) substrates. The phase formation, the grain size and morphology of the thin films were influenced by the addition of bismuth in excess. It was observed that the formation of single phase BBN for films was prepared with excess of bismuth up to 2 wt%. The films prepared with excess of the bismuth showed higher grain size and better dielectric properties. The 2 wt% bismuth excess BBN thin film exhibited dielectric constant of about 335 with a loss of 0.049 at a frequency of 100 kHz at room temperature.     

Effects of LiF addition on microstructure and dielectric properties of CaCu3Ti4O12 ceramics

The effects of small amounts of lithium fluoride sintering aid on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. CCTO polycrystalline ceramics with 0.5 and 1.0 mol% LiF, and without additive were prepared by solid state synthesis. Good densification (>90% of the theoretical density) was obtained for all prepared materials. Specimens without the sintering aid and sintered at 1090 °C exhibit secondary phases as an outcome of the decomposition reaction. The mean grain size is controlled by the amount of LiF in specimens containing the additive. Impedance spectroscopy measurements on CaCu₃Ti₄O₁₂ ceramics evidence the electrically heterogeneous nature of this material consisting of semiconductor grains along with insulating grain boundaries. The activation energy for grain boundary conduction is lower for specimens prepared with the additive, and the electric permittivity reached 53,000 for 0.5 mol% LiF containing CCTO.     

Effects of chemical additives on high-field electromechanical properties of PMN–PT–BT ceramics

A chemical additive method using sol–gel reactions was used to modify the composition and resultant properties of a commercially available 0.96(0.91Pb(Mg_1/3Nb_2/3)O₃–0.09PbTiO₃)–0.04 BaTiO₃ (PMN–PT–BT) ceramic. Without an additional ball-mixing process, several combinations of minor additives such as Fe, Ba, Sr, Zn, and Ti were incorporated by the chemical method. Weak- and high-field characteristics including dielectric properties, induced strain and polarization, and associated hystereses were evaluated for the samples sintered at 1200 °C for 4 h. All properties were found to depend on the chemical additives and temperature. Especially, the temperature dependence of high-field characteristics revealed different behavior from that reported for conventionally prepared samples. For example, the samples containing 0.5 wt.% SrO, 0.5 wt.% ZnO, and 0.5 wt.% TiO₂ did not exhibit a transition to piezoelectric behavior at the temperature expected from the dielectric measurements. Overall, the coating process has been successfully used to modify, and in some cases, enhance the high-field characteristics of PMN-based ceramics for electromechanical uses.     

Ultrahigh Q values and atmosphere-controlled sintering of Li2(1+x)Mg3ZrO6 microwave dielectric ceramics

Ultrahigh-Q Li_2(1+x)Mg₃ZrO₆ microwave dielectric ceramics were successfully prepared by means of atmosphere-controlled sintering through simultaneously adopting double crucibles and sacrificial powder. This technique played an effective role in suppressing the lithium volatilization and further promoting the formation of the liquid phase, as evidenced by the X-ray diffraction, microstructural observation and the density measurement. Both dense and even microstructure, and the suppression of detrimental secondary phases contributed to low-loss microwave dielectric ceramics with Q×f values of 150,000–300,000 GHz. Particularly, desirable microwave dielectric properties of ε_r=12.8, Q×f=307,319 GHz (@9.88 GHz), and τ_f=−35 ppm/°C were achieved in the x=0.06 sample as sintered at 1275 °C for 6 h.     

Low-temperature sintering and microwave dielectric properties of 3Z2B glass–Al2O3 composites

A potential low temperature co-fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and Al₂O₃ filler was investigated with regard to phase development and microwave dielectric properties as functions of the glass content and sintering temperature. The densification mechanism for 3Z2B–Al₂O₃ composites was reported. The linear shrinkage of 3Z2B glass–Al₂O₃ composites exhibited a typical one-stage densification behavior. XRD patterns showed that a new crystalline phase, ZnAl₂O₄ spinel, formed during densification, indicating that certain chemical reaction took place between the 3Z2B glass matrix and the alumina filler. Meanwhile, several zinc borate phases, including 4ZnO·3B₂O₃, crystallized from the glass matrix. Both of the reaction product phase and crystallization phases played an important role in improving the microwave dielectric properties of composites. The optimal composition sintered at 850–950 °C showed excellent microwave dielectric properties: ?_r = ∼5.0, Q·f₀ = ∼8000 GHz, and τ_f = ∼−32 ppm/°C at ∼7.0 GHz.     

Permittivity and temperature response of complex niobate perovskite dielectrics

Dielectric materials in the barium strontium zinc cobalt niobate system have been prepared to explore the consequences of independent variation of the population of the A and B sites in the perovskite structure. Results for the temperature coefficient of the resonant frequency follow the empirical relationship with the “t” factor established by Reaney. Permittivity results show deviation from linear behaviour with composition as previously observed by Kim. By comparing ionic polarisibilities calculated from the measured permittivities using the Clausius–Mossotti equation and from the ion additivity rule we show that the anomalous results are those for the high barium compositions. We demonstrate that these can be explained by compression of the A site ions and propose a simple calculation to estimate the extent of this effect which agrees well with the experimental results.     

Characterization of submicrometer-sized NiZn ferrite prepared by spark plasma sintering

High-density submicrometer-sized Ni_0.5Zn_0.5Fe₂O₄ ferrite ceramics were prepared by spark plasma sintering in conjunction with sufficient high energy ball milling. They were evaluated by different characterization techniques such as X-ray diffraction, scanning electron microscopy, and dielectric and magnetic measurements. All samples prepared at sintering temperatures ranging from 850 to 925 °C exhibit a single spinel phase and their relative densities and grain sizes range from 90% to 99% and ~100 nm to ~300 nm, respectively. The dielectric constant increases with decreasing grain size until ~250 nm, and then decreases dramatically with further decreasing grain size. The saturation magnetization increases continuously with increasing grain size/density but the magnetic coercivity decreases. The highest dielectric constant and saturation magnetization at room temperature are approximately 1.0×10⁵ and 84.4 emu/g, respectively, while the lowest magnetic coercivity is only around 15 Oe. These outstanding properties may be associated with high density and uniform microstructure created by spark plasma sintering. Therefore, the spark plasma sintering is a promising technique for fabricating high-quality NiZn ferrites with high saturation magnetization and low coercivity.     

Effect of sintering regimes on the microstructure and magnetic properties of LiTiZn ferrite ceramics

In present work, the influence of sintering regimes on the microstructure, saturation magnetization, density and porosity, the grain size, the Curie point, and the temperature dependence of the initial permeability of LiTiZn ferrite ceramics was investigated. Ceramics was prepared by a standard ceramic technique. The formation of a single-phase cubic spinel structure was confirmed by XRD analysis. The Curie point was determined from both the temperature dependences of the initial permeability and the method of thermogravimetric measurements in a magnetic field. Density/porosity and the grain size, the Curie point and magnetization are sensitive to the sintering regime. The initial permeability of ferrite decreases with sintering temperature (in the range of 1010–1150?°С) and grain size increasing that contradicts the generally accepted Globus and Smith-Wijn theories. A possible reason of such behavior is the formation of intragranular pores growing with the increase in the sintering temperature and inhibiting the domain wall motion inside the grain. These results correspond to the porosity of the investigated ferrite ceramic samples, which grows with sintering temperature increasing.The non-stoichiometry arising due to evaporation of lithium and zinc oxides at temperature above 1010?°C affects the initial permeability. In this work, a qualitative assessment of the defective state of ferrite samples obtained under various sintering regimes was given.     

Effect of Bi2O3 additives on sintering and microwave dielectric behavior of La(Mg0.5Ti0.5)O3 ceramics

Bi₂O₃ was selected as liquid phase sintering aid to lower the sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics. The sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics is generally high, about 1600 °C. However, the sintering temperature was significantly lowered about 275 °C from 1600 °C to 1325 °C by incorporating in 15 mol% Bi₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (?_r) value of 40.1, a quality factor (Q × f) value of 60,231 GHz, and the temperature coefficient (τ_f) value of 70.1 ppm/°C. During all addition ranges, the relative dielectric constants (?_r) were different and ranged from 32.0 to 41.9, the quality factors (Q × f) were distributed in the range of 928–60,231 GHz, and the temperature coefficient (τ_f) varies from 0.3 ppm/°C to 70.3 ppm/°C. Noticeably, a nearly zero τ_f can be found for doping 5 mol% Bi₂O₃ sintering at 1325 °C. It implies that nearly zero τ_f can be achieved by appropriately adjusting the amount of Bi₂O₃ additions and sintering temperature for La(Mg_0.5Ti_0.5)O₃ ceramics.     

The influence of sintering aids for Nd(Mg0.5Ti0.5)O3 microwave dielectric ceramics properties

The influence of various sintering aids on the microwave dielectric properties and the structure of Nd(Mg_0.5Ti_0.5)O₃ ceramics were investigated systematically. B₂O₃, Bi₂O₃, and V₂O₅ were selected as liquid-phase sintering aids to lower the sintering temperature. The sintered Nd(Mg_0.5Ti_0.5)O₃ ceramics are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and microwave dielectric properties. The sintering temperature of Nd(Mg_0.5Ti_0.5)O₃ microwave dielectric ceramics is generally high, about 1500 °C. However, the sintering temperature was significantly lowered about 175 °C from 1500 °C to 1325 °C by incorporating in 10 mol% B₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (_r) value of 26.2, a quality factor (Q × f) value of 61,307 (at 9.63 GHz), and τ_f value of −45.5 ppm/°C. NdVO₄ secondary phase was observed at 10 mol% V₂O₅ addition in the sintering temperature range of 1300–1325 °C, which led the degradation in microwave dielectric properties. The microwave dielectric properties as well as grain sizes, grain morphology, and bulk density were greatly dependent on sintering temperature and various sintering aids. In this study, it is found that Nd(Mg_0.5Ti_0.5)O₃ incorporated with 10 mol% B₂O₃ with lower sintering temperature and excellent dielectric microwave properties may be suggested for application in microwave communication devices. The use of liquid-phase sintering, the liquid formed during firing normally remains as a grain boundary phase on cooling. This grain boundary phase can cause a deterioration of the microwave properties. Therefore, the selection of a suitable sintering aid is extremely important.     

Adjustable dielectric properties of Li2CuxZn1−xTi3O8 (x=0 to 1) ceramics with low sintering temperature

Single-phase dielectric ceramics Li₂Cu_xZn_1−xTi₃O₈ (x=0–1) were synthesized by the conventional solid-state ceramic route. All the solid solutions adopted Li₂MTi₃O₈ cubic spinel structure in which Li/M and Ti show 1:3 order in octahedral sites whereas Li and M are distributed randomly in tetrahedral sites with the degree of Li/M cation mixing varying from 0.5 to 0.3. The substitution of Cu for Zn effectively lowered the sintering temperatures of the ceramics from 1050 to 850 °C and significantly affected the dielectric properties. As x increased from 0 to 0.5, τ_f gradually increased while the dielectric constant (ε_r) and quality factor value (Q×f) gradually decreased, and a near-zero τ_f of 1.6 ppm/°C with ε_r of 25.2, Q×f of 32,100 GHz could be achieved for Li₂Cu_0.1Zn_0.9Ti₃O₈ ceramic sintered at 950 °C, which make it become an attractive promising candidate for LTCC application. As x increases from 0.5 to 1, the dielectric loss significantly increases with AC conductivity increasing up to 2.3×10⁻⁴ S/cm (at 1 MHz).     

Effect of Ce and La substitution on dielectric properties of bismuth titanate ceramics

Effect of Ce and La substitution on the microstructure and dielectric properties of bismuth titanate (BT) ceramics was investigated. Bismuth titanate ceramics (Bi_4−xA_xTi₃O₁₂) (A = Ce or La; x = 0, 0.5, 1) were processed by sintering of pressed pellets, prepared from nanopowder synthesized by the modified sol-gel method. Pure and La modified bismuth titanate ceramics have single Bi₄Ti₃O₁₂ phase of Aurivillius type, whereas a small amount of Bi₂Ti₂O₇ pyrochlore phase appears in Ce modified bismuth titanate ceramics. In the same time addition of La and Ce improved sinterability of BT ceramics. The results of the measurement of dielectric constant and loss tangent at different frequencies (100 Hz-1 MHz) as a function of temperature reveal that Ce modified ceramics has a diffuse phase transition. Temperature T_m, corresponding to the maximum value of the dielectric constant, is shifted to higher temperature and the maximum value of the dielectric constant is decreased with increasing frequency, which indicate that relaxor behavior is caused by Ce substitution.