The dielectric properties for (Nb,In,B) co-doped rutile TiO2 ceramics

Recently, colossal permittivities (~10⁵) and low loss factors (<0.1) were reported in (Nb+In) co-doped rutile TiO₂ ceramics, which have attracted considerable attention. In this work, (Nb,In,B) co-doped rutile TiO₂ ceramics were investigated for achieving temperature- and frequency- stable dielectric properties in TiO₂ based colossal dielectric ceramics. The (Nb,In,B) co-doped rutile TiO₂ ceramics were prepared by conventional solid-state reaction method. The microstructures, dielectric properties and complex impedance of 1 mol.% (Nb+In) co-doped rutile TiO₂ (TINO) and xwt% B₂O₃ (x=0.5, 1, 2 and 4) doped TINO were systematically investigated and compared. It was found that by doping B₂O₃ the sintering temperature of TINO ceramics can be reduced by 100 °C. Meanwhile, the dielectric loss of TINO ceramics was decreased by doping B₂O₃. In the ₂wt% B₂O₃ doped TINO ceramics, the dielectric permittivity kept a high value of >2.0×10⁵ and the dielectric loss was lower than 0.1 in a frequency range of 10²−10⁵ Hz and a temperature range of 25–200 °C.     

Giant permittivity up to 100 MHz in La and Nb co-doped rutile TiO2 ceramics

Dielectric spectroscopy was carried out for reduced and stoichiometric La_0.0025Nb_0.0025Ti_0.995O₂ ceramics synthesized by sintering in different atmospheres. A giant permittivity (~1 × 10⁴) was obtained at a frequency of 100 MHz and temperature range from 170 to 350 K. Three dielectric relaxation mechanisms were observed within the temperature range of 10-300 K via dielectric spectroscopy. A low temperature dipole relaxation peak (in the temperature range of 10-30 K) in the spectra was identified to be associated with the giant permittivity specifically measured at 100 MHz. The origin of such giant permittivity was attributed to dipole orientation polarization. Hopping polaron and interfacial effect contributed to giant permittivity. After annealing treatment, all the relaxation contributions were weakened. Low dielectric loss was attributed to high resistance of grain and grain boundaries. Annealing in ambient conditions led to decreased relaxation times which gives the signature of decreased concentration of oxygen vacancies and Ti³⁺. Dipoles which were related to oxygen vacancies and Ti³⁺, resulted in giant permittivity up to 100 MHz.     

Mechanical,wear, and dielectric behavior of TiO2 reinforced high-density polyethylene composites

Almost fully dense high-density polyethylene (HDPE) reinforced with submicron-sized titanium dioxide (TiO₂) ceramic filler (up to 40 vol %) was fabricated using compression molding. More than 98.5% ρ_th (theoretical density) could be obtained for all the HDPE compositions and its measured density varied between 0.94 and 2.25 g cc⁻¹. The hardness of HDPE increased considerably from 32.6 to 69 MPa (i.e., by two times) with the addition of 40 vol % TiO₂. The compression strength (19.03–34.16 MPa) and modulus of elasticity (0.49–1.05 GPa) of HDPE were also found to increase with the addition of TiO₂ filler. However, the HDPE exhibited good ductility (59% strain) up to 20 vol % TiO₂ and it was reduced with the further addition of TiO₂. The strain decreased drastically to 7.6% for HDPE-40 vol % TiO₂. Addition of TiO₂ filler leads to a considerable decrease in wear rate and coefficient of friction (COF). The wear studies revealed that the HDPE-40% TiO₂ composite exhibited a low wear rate of 1.82 × 10⁻⁵ mm³ N m⁻¹ and COF of 0.13. The dielectric constant of HDPE (at 10 kHz) was also considerably increased from 5.31 to 20.02 with the addition of TiO₂ up to 40 vol %. Achievement of such high dielectric constant for HDPE materials is the highest ever reported for HDPE. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47610.     

Medium dielectric constant and low-loss PTFE composites filled with MgO-LiF co-doped Li2TiO3 particles

In this work, we presented a simple strategy to fabricate medium dielectric constant and low-loss composites for microwave substrate applications. MgO-LiF co-doped Li₂TiO₃ (LT) powders were fabricated by the solid-state reaction route and modified by perfluorooctyltriethoxysilane (F8261). The LT/polytetrafluoroethylene (PTFE) composites were fabricated by cold pressing and hot treatment. The XPS and contact angle analysis indicated that the fluorinated group was introduced to LT particle successfully. The effects of modified LT powders content on the dielectric, thermal, and mechanical properties of composites were investigated. As the modified LT content increases, the dielectric constant, dielectric loss, and temperature coefficient of dielectric constant (τ_ε) increase while the bending strength and coefficient of thermal expansion (CTE) decrease, which is attributed to the higher dielectric constant of LT ceramic, more pores, stable τ_ε of LT ceramic, interface defects and low CTE of LT ceramic, respectively. The composites with 60 wt % LT exhibit the best microwave dielectric properties: ε_r = 6.8, tanδ = 0.001, τ_ε = −29.6 ppm °C⁻¹ at 8 GHz and acceptable coefficient of thermal expansion (28.3 ppm °C⁻¹). Therefore, modified LT powders filled PTFE composites are potential materials for high-frequency microwave substrate applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47980.     

Controllable low-temperature flash sintering and giant dielectric performance of (Zn,Ta) co-doped TiO2 ceramics

In this study, the challenge of high-temperature and long-time sintering of (Zn, Ta) co-doped TiO₂ ceramics is solved successfully using flash sintering technology. Joule heating and a high heating rate make the sample compact rapidly at low temperatures (1050 °C in 24 min). When the electric field was equal to 200 V/cm, high permittivity (ε' ～ 1.32 × 10⁴), low dielectric loss tangent (tan δ ～ 0.27), and nonlinear coefficient ($\alpha$ ～ 5.8) values were obtained. Flash sintered samples have more free electrons, resulting in a high dielectric constant. Further, the higher the electric field, the smaller the grain resistance of the sample; this condition is conducive to reducing dielectric loss. giant dielectric performance is explained by the combined action of the electron-pinned defect dipole theory and the internal barrier layer capacitance effect. Therefore, this study provides a promising prospect for the green preparation of co-doped TiO₂ giant dielectric ceramics.     

Microstructure and broadband dielectric properties of Zn2SiO4 ceramics with nano-sized TiO2 addition

Zn₂SiO₄ ceramics with nano-sized TiO₂ addition (ZST) were synthesized by conventional solid state method. The association between the new composite's microstructures and dielectric properties reveals that reduced pores, increased density and average grain sizes with increasing sintering temperatures, have contributed to the increased permittivities at kHz and microwave bands; the decrease of the permittivities at 1275 °C is due to the form of twin planes. At the terahertz band, the competition of generating oxygen vacancies and forming them into twin crystallographic shear planes dominates the change of permittivities: the crystallographic shear planes decrease the permittivity at the sintering temperature 1225 °C and 1250 °C, and the high-rate generation of oxygen vacancies at 1275 °C increases the permittivities. The ZST ceramics demonstrate stable permittivity and low dielectric losses (<10^–3 from 10 kHz to microwave band; and <10^–2 at THz range); and the temperature coefficient of resonant frequency is optimized to close zero. These advanced dielectric properties and low sintering temperature (<1300 °C) provide the ZST ceramics great potential in designing microwave and THz devices.     

Good thermal stability,giant permittivity,and low dielectric loss for X9R-type (Ag1/4Nb3/4)0.005Ti0.995O2 ceramics

With the intense demand of the developing microelectronics market, the study of giant permittivity dielectric materials is being promoted. However, it is difficult to obtain suitable dielectric materials for such applications, especially due to high dielectric loss at low frequencies. In this work, Ag+Nb codoped TiO₂ ceramics were designed and fabricated in a conventional solid reaction by sintering at 1290-1340°C for 5-10 hours. The issue of how the microstructure and dielectric properties of (Ag_1/4Nb_3/4)_0.005Ti_0.995O₂ ceramics are affected by the sintering conditions was discussed. By optimizing sintering conditions, a dense microstructure, a high dielectric constant (ε_r ≈ 9410), and a low dielectric loss (tanδ ≈ 0.037) at 1 kHz were achieved. Most importantly, the temperature coefficient value of ε_r at different frequencies remained stable between −14.3% and 13.7% within the temperature range from −190 to 200°C, which has potential applications in X9R capacitor.     

Structure,infrared spectra and microwave dielectric properties of the novel Eu2TiO5 ceramics

The microwave dielectric properties of Eu₂TiO₅ ceramic prepared by a conventional solid-state method were investigated for the first time. An orthorhombic structure with Pnam space group was obtained from x-ray diffraction. On the basis of P-V-L chemical bond theory and refined lattice parameters, the bond parameters of bond ionicity, lattice energy, bond energy, and coefficient of thermal expansion of Eu₂TiO₅ were computed. The relationship between chemical bond characteristics and microwave dielectric properties was discussed. Besides, far-infrared reflective spectra indicated the absorption of structural phonon oscillation might be the main contribution to polarization for Eu₂TiO₅ ceramic. Eu₂TiO₅ ceramic sintered at 1300°C for 6 hours possessed excellent microwave dielectric properties of ε_r ~ 14.4 ± 0.2, Q × f ~ 21 000 ± 500 GHz, and τ_f  ~ −10 ± 2 ppm/°C.     

Microstructure,colossal permittivity,and humidity sensitivity of (Na,Nb) co-doped rutile TiO2 ceramics

(Na_0.25Nb_0.75)_xTi_1−xO₂ (NNTO) ceramics (x = 0, 0.005, 0.01, 0.02, and 0.05) were prepared by the conventional solid-state reaction. The microstructure, dielectric, and humidity sensitivity of the ceramics were systematically investigated. Results showed that all ceramics exhibit pure rutile TiO₂ phase with dense microstructures. Co-doping of (Na, Nb) can effectively improve the microstructure homogeneity of the ceramics. When the doping level x ≥ 0.01, the co-doped samples show colossal permittivity higher than 10⁴ and dielectric loss tangent lower than 0.38. This dielectric behavior features the merit of both frequency and temperature stability in the range of 10²-10⁶ Hz and 100-300 K, respectively. The co-doped ceramics were found to be sensitive to the environment moisture. The humidity sensitivity incurs a Maxwell-Wagner relaxation near room temperature, which further enhances the dielectric permittivity. Excellent humidity sensitive properties of sensitivity to be 102.6 pF/%RH, response/recovery time to be 115/20 seconds, as well as good repeatability, were achieved in the sample with the doping level x = 0.05. This work underscores that the room temperature dielectric properties of doubly doped TiO₂ system depends strongly on the environmental condition and suggests that the (Na + Nb) co-doped TiO₂ ceramics might be promising humidity sensing materials.     

Ti基碳氮共掺杂TiO2的制备、结构表征及光催化氯苯废气性能

以钛酸四丁酯为钛源、葡萄糖和尿素作为掺杂剂,采用水热-溶胶凝胶法制备了碳氮共掺杂TiO₂光催化剂,研究了该催化剂的结构特性及其对氯苯(CB)废气的转化性能。响应面法分析了C、N与钛酸四丁酯的添加比例对TiO₂催化CB的影响,获得了C和Ti物质的量比0.49、N和Ti物质的量比0.28时,该催化剂对CB的转化效率相对较高。利用XRD、TEM等对催化剂结构以及形貌进行表征表明:C/N共掺杂TiO₂为锐钛矿和金红石混合晶型,比表面积较大,吸收波长红移至500 nm。在反应介质相对湿度10%、CB初始浓度 50 mg·m^-3、反应时间60 s时,催化转化率93.5%;制备的催化剂在相对湿度10%~60%范围内对CB均具有较好的去除效果。稳定性实验表明,连续测试10 h对CB的转化率略微下降。     

钨、氮共掺杂TiO2的制备及其光催化性能研究

为了更好的利用太阳能,以钛酸正丁酯为前驱体,硝酸铵和钨酸铵为掺杂离子给体,通过溶胶-凝胶法,室温下成功制备了纯TiO2和钨、氮掺杂和共掺杂的TiO2光催化剂.表征结果显示,共掺杂催化剂为锐钛矿型,外观呈球形,感光范围拓展到可见光区域.以甲基橙为降解物,氙灯为模拟太阳光光源,进行光催化降解实验,钨、氮共掺杂TiO2在光照...     

Influence of Zr dopant on polarization in rutile (In0.5Nb0.5)0.005(Ti1-xZrx)0.995O2 ceramics

(In_0.5Nb_0.5)_0.005(Ti_1-xZr_x)_0.995O₂ (INZT, x = 0-0.10) ceramics were synthesized using a conventional sintering method, and the effects of Zr content on the microstructures, dielectric properties and electron-pinned defect-dipoles (EPDD) polarization of the resultant products were investigated. The solubility limit of INZT was x = 0.075, and a secondary ZrTiO₄ phase appeared at x = 0.10. Ceramics with x = 0-0.10 exhibited excellent dielectric properties, ie, colossal permittivity (CP, εʹ > 10³) and low dielectric loss (tanδ < 0.1), over a wide range of frequencies (10⁰-10⁶ Hz at 300 K) and temperatures (50-350 K at 1 kHz). The dielectric spectra and XPS results confirmed that the CP property of the ceramics could be ascribed to their EPDD polarization. The activation energy (E_a) for EPDD polarization was continuously enhanced by increasing x values. EPDD relaxation parameters at different x values were revealed using Cole-Cole equation fitting. Moreover, α, which characterize the relaxation time τ distribution, increased with x values, thus indicating that Zr was involved in and affected electron localized states. The high E_a, temperature T_p of the peak εʹʹ at 1 kHz, and dielectric relaxation time τ_p at 30 K were related to increases in hopping distance of electrons among defect clusters with Zr addition.     

A low-permittivity microwave dielectric ceramic BaZnP2O7 and its performance modification

Complex pyrophosphates compounds have attracted much attention as promising candidates for substrate applications. In the work, a low-permittivity BaZnP₂O₇ ceramic was synthesized through solid-state reaction. The pure phase BaZnP₂O₇ was crystallized in the triclinic P−1 space group. Excellent microwave dielectric properties of the BaZnP₂O₇ ceramic with ε_r = 8.23, Qf = 56170 GHz, and τ_f = −28.7 ppm/°C were obtained at 870°C for 4 h. The substitution of Mg²⁺ for Zn²⁺ was found to have positive effects on grain morphology and dielectric properties. Optimized performance of ε_r = 8.21, Qf = 84760 GHz, and τ_f = −21.9 ppm/°C was yielded at 900°C for the BaZn₀.₉₈Mg_0.02P₂O₇ ceramic. Intrinsic dielectric properties of BaZn_1-xMg_xP₂O₇ ceramics were studied via Clausius–Mossotti equation and complex chemical bond theory.     

N、Mo共掺杂TiO_2光催化剂的制备及对亚甲基蓝降解性能研究

以硫脲、钼酸铵和钛酸四丁酯为原料,利用溶胶-凝胶法制备了未掺杂的和N、Mo共掺杂的TiO2光催化剂。用紫外-可见吸收光谱对制备的催化剂样品进行了表征,考察了不同条件下光催化剂对亚甲基蓝溶液的光催化活性。试验结果表明,N、Mo共掺杂使TiO2催化剂的吸收带边位置发生了红移;在可见光条件下,0.125 gN、Mo共掺杂TiO2(n(N)∶n(Mo)=2∶1)、pH值为6.20、温度为30℃的体系对质量浓度为20 mg/L的亚甲基蓝溶液的脱色效果最好。     

Dielectric and electric relaxations induced by the complex defect clusters in (Yb+Nb) co‐doped rutile TiO2 ceramics

The effect of the Yb+Nb substitution for Ti on the microstructure, crystal structures, and dielectric properties of (Yb_1/2Nb_1/2)_xTi_1?xO₂ (0.01≤x≤0.1) ceramics is investigated in this study. The results reveal that the solid solubility limit of the (Yb_1/2Nb_1/2)_xTi_1?xO₂ ceramics is x=0.07, and the average grain sizes considerably decrease from 12 μm to 6 μm with x increasing from 0.01 to 0.1. Three types of dielectric relaxations are observed at temperature ranges of 10‐30 K, 80‐180 K, and 260‐300 K, caused by the electron‐pinned defect dipoles, polaron hopping, and interfacial polarizations, respectively. The conduction mechanism changes from nearest‐neighbor‐hopping to polaron hopping mechanism, which is confirmed by ac conductivity measurements. The present work indentifies the correlation between the colossal permittivity and polaron hopping process in the titled compound.     

Structural,dielectric and mechanical behaviors of (La,Nb) Co-doped TiO2/Silicone rubber composites

Ceramic/polymer composites have great potential to achieve the concomitant enhancement of both dielectric constant and breakdown field while maintaining other superior properties of the polymer matrix, ideal for elastomer sensors, actuators, capacitive energy storage, and many other applications. However, material incompatibility between the ceramic filler and the polymer matrix often leads to void formation, particle aggregation and phase separation, with significantly degraded performance. Herein, through surface modification, co-doped TiO₂ particles were uniformly dispersed and bridged onto the silicone rubber matrix via a silane coupling agent for fabricating composites via mechanical mixing and hot-pressing. The synthesized composites exhibit enhanced dielectric constant, increased from 2.78 to 5.06 when 50 wt% co-doped TiO₂ particles are incorporated. Their dielectric loss is less than 0.001 in a broad frequency range. Theoretical modelling and experimental results reveal that the morphology and dispersion state of co-doped TiO₂ particles were crucial to the dielectric properties of the silicone rubber-based composites. Besides, the composites are thermally stable up to 400 °C. Significantly increased tensile strength (612 kPa) and elongation at break (330%) were obtained for the composite incorporated with 30 wt% co-doped TiO₂ particles, accompanied by a moderate increased elastic module (540 kPa). Such composites have the potential for different applications.     

Effects of Sn substitution on the crystal structures,microstructures, and microwave dielectric properties of Ce2Zr3(MoO4)9 ceramics

A series of Ce₂(Zr_1?xSn_x)₃(MoO₄)₉ (0.02 ≤ x ≤ 0.1) (CZ_1?xS_xM) ceramics were synthesized to investigate the effect of Sn⁴⁺ doping on the crystal structure, chemical bond parameters, and dielectric properties of Ce₂Zr₃(MoO₄)₉ ceramics. X-ray diffraction patterns illustrated the formation of the single-phase trigonal system solid solution in all samples. Rietveld refinement result showed that the lattice volume decreased linearly, which can be explained by the fact that the effective radius of Sn ion is smaller than that of Zr ion. As the Sn content increased, scanning electron microscope images showed that the CZ_1?xS_xM ceramics transformed from bar-like grains to disk-like grains and the grain size declined gradually. The structure–property correlation was estimated by using P–V-L theory; the descending ε_r was mainly consistent with the reduced polarizability and total bond ionicity. The Q × f was associated with the lattice energy of the Ce–O1 bond. The change of τ_f value was mainly attributed to the bond energy (E_Mo1–O1 and E_Mo1–O4) and the coefficients of thermal expansion (α_Mo1–O1 and α_Mo1–O4). Infrared analysis indicated that the dielectric properties of the CZ_1?xS_xM ceramics were primarily ascribed to the absorption of phonon oscillation. Notably, when x = 0.08, outstanding microwave dielectric properties could be achieved, namely, ε_r = 10.22, Q × f = 72,390 GHz, τ_f = ?7.54 ppm/°C.     

CuGaO2/TiO2 heterostructure nanosheets: Synthesis,enhanced photocatalytic performance,and underlying mechanism

Effective separation and fast transport of photogenerated carriers are vital links determining the photocatalytic performance. Heterostructure constructed by two complementary semiconductors is a feasible strategy to achieve this goal. By one-pot hydrothermal method, 0D-TiO₂ nanoparticles are loaded onto 2D-CuGaO₂ nanosheets, forming a mixed dimension, closely combined heterostructure. The photocurrent density of CuGaO₂/TiO₂ heterostructure is ∼16.6 μA/cm², which is 1.24 times higher than that of pristine CuGaO₂ nanosheets (∼13.4 μA/cm²) and 15 times higher than that of TiO₂ (∼1.1 μA/cm²). In the tetracycline hydrochloride degradation experiment, the degradation efficiency of tetracycline hydrochloride by CuGaO₂/TiO₂ heterostructure reached 99% within 90 min, which was 1.2 times the degradation efficiency of CuGaO₂ nanoparticles (82%) and 20.2 times the degradation rate of TiO₂ (4.9%). A series of experimental characterizations combined with density functional theory calculations revealed that it is the built-in electric field in the CuGaO₂/TiO₂ interface region that drives the photogenerated electron–hole pairs to travel in the opposite direction, thus inhibiting their recombination. Furthermore, the energy band offset of the CuGaO₂/TiO₂ interface makes it easier for the photogenerated holes and electrons to gather onto the valence band of the CuGaO₂ nanosheets and the conduction band of the TiO₂ nanoparticles, respectively. Therefore, appropriate interface lattice matching, suitable configuration of band gap and band edge positions, and strong opposite drive of interface electric field enable CuGaO₂/TiO₂ heterostructure to achieve wide spectral response and effective separation of photogenerated electron–hole pairs at the same time.     

Effect of nano‐TiO2 surface modification on polarization characteristics and corona aging performance of polyimide nano‐composites

Using coupling agent isocyanatopropyltriethoxysilane (ICTOS) to modified nano‐TiO_2, the polyimide (PI) with different titanium dioxide (TiO₂) contents (0, 1, 2, 3, 4, and 5 wt %) doped nano‐composites were prepared by sol–gel method (PI/TiO_{2 ICTOS} composites). The effect of ICTOS modification on polarization and time‐to‐breakdown properties of composites were investigated by thermally stimulated depolarization current (TSDC) method, dielectric, and Corona aging measurements. The TSDC spectra show that ICTOS modification enhanced α‐peak intensity and make β‐peak disappear in composites. Relevant trap parameters were calculated by an approximate model, and the results indicate that introduction of ICTOS is effective for the charge carrier traps, activation energy distribution in composites. Corona aging measurement show corona resistance was also sufficient improved in PI/TiO_{2 ICTOS} composites. The changes of activation energy and intensity of traps in composites may be responsible for the corona resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45101.