Microstructural and optical properties of the ZnS ceramics sintered by vacuum hot-pressing using hydrothermally synthesized ZnS powders

ZnS nanopowders annealed at low temperatures (≤550?°C) have a pure cubic structure, while a small amount of hexagonal phase formed in specimens annealed at temperatures ≥700?°C. The particle sizes of the ZnS nanopowders increased with the annealing temperature. ZnS ceramics that were sintered using ZnS nanopowders annealed at low temperatures (≤550?°C) exhibited low transmittance, because of their porous microstructure. ZnS ceramics that were synthesized using ZnS powders annealed at high temperatures (≥800?°C) containing large agglomerated particles, also exhibited low transmittance, due to the presence of a liquid phase. A carbonate absorption band was found from the ZnS ceramics with small grains, because carbon ions diffused from the graphite mold into the ZnS ceramics during sintering, probably through the grain boundaries, and formed carbonates. A ZnS ceramic that was sintered at 1020?°C using the nanopowders annealed at 750?°C exhibited dense microstructure, with a large transmittance, 68%, in the wavelength range 6.0–12?μm.     

Ordering of fluorite-type phases in erbium-doped oxyfluoride glass ceramics

In this study, novel transparent Er³⁺ doped glass ceramics were prepared from melt-quenched oxyfluoride glasses with general composition of Na₂O-NaF-BaF₂-YbF₃-Al₂O₃-SiO₂. The crystallization of fluorite (BaF₂, BaF₂-YbF₃, NaF-BaF₂-YbF₃ and Na_0.5-xYb_0.5+xF_2+2x) and distorted fluorite (rhombohedral Ba₄Yb₃F₁₇ and tetragonal NaF-BaF₂-YbF₃) phases was analysed in glass ceramics with different BaF₂ and YbF₃ ratio. The phase composition and microstructure were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Intense red upconversion luminescence (UCL) was detected under near-infrared excitation resulting from three photon upconversion followed by cross-relaxation between Er³⁺ and Yb³⁺ ions.The local environment of Er³⁺ ions in fluorite and distorted phases was analysed using site-selective spectroscopy. The Er³⁺ ions were found to act as nucleation centres in the glass ceramics containing BaF₂. The phase transition from metastable fluorite to rhombohedrally and tetragonally distorted fluorite phases was detected using Er³⁺ ions as a probe.     

Modified structural,optical, magnetic and ferroelectric properties in (1-x)BaTiO3-xBaCo0.5Nb0.5O3-δ ceramics

Lead-free perovskite ceramics with the formula of (1-x)BaTiO₃-xBaCo_0.5Nb_0.5O_3-δ ((1-x)BT-xBCN), exhibit structural phase transition, modified band-gap (E_g), ferromagnetic and ferroelectric orders at room-temperature (RT). All ceramics have no impurity phase but the structural transition from tetragonal to cubic phase is observed with the increase of x. A possible mechanism is proposed to explain the variation of crystal structure. Raman scattering analysis not only proves the existence of doping-induced phase transition but also indicates the changed bonding vibration modes between adjacent atoms. The appearance of two band-gaps in doping samples, the low E_g is about 1.3 eV, obviously smaller than that of 3.2 eV for pure BaTiO₃ (BT), which is attributed to the electronic orbital of Co 3d within the gap of BT. Moreover, the RT ferromagnetic behavior is obtained at x = 0.05, which can be interpreted via the F center exchange model. These results show the potential applications for perovskite oxides on solar energy conversion apparatus and multiferroic devices.     

Phase structure,ferroelectric properties,and electric field-induced large strain in lead-free 0.99[(1−x)(Bi0.5Na0.5)TiO3-x(Bi0.5K0.5)TiO3]–0.01Ta piezoelectric ceramics

Lead-free 0.99[(1−x)(Bi_0.5Na_0.5)TiO₃-x(Bi_0.5K_0.5)TiO₃]–0.01Ta piezoelectric ceramics were prepared by a conventional solid-state reaction process. The ferroelectric properties, and strain behaviors were characterized. Increase of the (Bi_0.5K_0.5)TiO₃ content induces a phase transition from coexistence of ferroelectric tetragonal and rhombohedral to a relaxor pseudocubic phase. Accordingly, the ferroelectric order is disrupted significantly with the increase of (Bi_0.5K_0.5)TiO₃ content and the destabilization of the ferroelectric order is accompanied by an enhancement of the unipolar strain, which peaks at a value of 0.35% (corresponding to a large signal d₃₃ of 438 pm/V) in samples with 20 mol% (Bi_0.5K_0.5)TiO₃ content. Temperature dependent measurements of both polarization and strain from room temperature to 120 °C suggested that the origin of the large strain is due to a reversible field-induced nonpolar pseudocubic-to-polar ferroelectric phase transformation.     

Evolving antiferroelectric stability and phase transition behavior in NaNbO3-BaZrO3-CaZrO3 lead-free ceramics

The stability of antiferroelectricity in NaNbO₃ ceramics was found to evolve with co-doping x mol% CaZrO₃ and 6 mol% BaZrO₃, from a dominant ferroelectric (FE) orthorhombic Q phase (x = 0) to a gradually stabilized antiferroelectric (AFE) orthorhombic P phase owing to different ionic radii of Ba and Ca ions. Although a complete AFE P phase appears at x = 0.5, the field induced AFE-FE phase transformation is irreversible at first, and then becomes partially reversible at x = 1 and finally completely reversible at x = 3. The above-mentioned change process proves to be associated with the enhancing stability of antiferroelectricity with x, as evidenced by means of dielectric, polarization and strain properties as well as in/ex-situ synchrotron x-ray diffraction and Raman spectra. A composition-field phase diagram for the NN-based lead-free AFE ceramic was constructed on basis of the phase structural change, which would provide a clear understanding of how ion doping influences its antiferroelectricity.     

透明陶瓷的研究进展

综述了影响陶瓷透明度的因素。分别介绍了红外陶瓷、激光陶瓷、闪烁陶瓷,并对他们未来的发展趋势进行简要的综述。     

Electric field induced phase transition and accompanying giant poling strain in lead-free NaNbO3-BaZrO3 ceramics

A series of phase transitions in (1-x)NaNbO₃-xBaZrO₃ ((1-x)NN-xBZ) ceramics was observed from antiferroelectric orthorhombic phase to ferroelectric orthorhombic phase and finally into ferroelectric rhombohedral phase with increasing x. An electric field induced irreversible phase transition was found in different compositions, irrespective of their virgin phase structures. Particularly, an antiferroelectric orthorhombic phase is irreversibly transformed into a ferroelectric monoclinic phase within 0.02?≤?x?≤?0.05, leading to a giant poling strain of ～0.58%. This is much larger than that observed in ferroelectric orthorhombic (0.06?≤?x?≤?0.07) and rhombohedral phases (0.08?≤?x?≤?0.11) suffering from an irreversible ferroelectric-ferroelectric (monoclinic) phase transition. The synchrotron x-ray diffraction and the measurement of longitudinal and transverse strains suggest that this irreversible phase transition should involve not only a distinct volume expansion, but also an obvious lattice elongation. The present study demonstrates a unique nature of the composition and field dependent phase stability and an underlying mechanism of giant poling strains in NN-BZ ceramics.     

Enhanced thermal stability of piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O3 systems through tailoring phase transition behavior

Good thermal stability in lead-free BaTiO₃ ceramics is important for their applications above room temperature. In this study, thermal stable piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O₃ ceramics was enhanced by tailoring their phase transition behaviors. Comparison between (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ and (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ revealed that latter system at y?=?0.80 had much better thermal stable piezoelectric coefficient than the former at x?=?0.45. Both systems crystalized in tetragonal to orthorhombic phase boundary at room temperature. The phase transition temperature and degree of diffusion were adjusted by Ca and Zr ions contents and demonstrated great influence on temperature dependent dielectric permittivity, hysteresis loops, and in-situ domain structures. The improved thermal stability of (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ prepared at y?=?0.80 was linked to its higher paraelectric to ferroelectric phase transition temperature (T_m?=?115.7?°C) and less degree of diffusion (degree of diffusion constant γ?=?1.35). By comparison, (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ prepared at x?=?0.45 revealed T_m?=?81.3?°C and γ?=?1.65. Overall, these findings look promising for future stimulation of phase transition behaviors and design of piezoelectric materials with good thermal stabilities.     

透明陶瓷的制备技术及其透光因素的研究

简要地介绍了国内外透明陶瓷的制备技术,同时探讨了气孔和晶界组织结构等因素对透明陶瓷的透光性能的影响,并展望了透明陶瓷研究的发展趋势.     

Transparent AlON ceramic combined with VO2 thin film for infrared and terahertz smart window

Transparent AlON ceramics are intriguing window materials with excellent mechanical strength and superb optical transparency from the near ultraviolet to the mid-infrared range. However, previous studies focused their investigations in the visible range; therefore, the application of transparent AlON ceramics to tunable windows has yet to be reported. In this work, a VO₂ thin film with a characteristic semiconductor-metal phase transition (SMT) was fabricated on a transparent AlON ceramic, which exhibited remarkable tunable switching properties in the infrared and terahertz ranges. The transparent AlON ceramic was prepared by a two-step method, which included carbothermal reduction and pressureless sintering. The resulting ceramic exhibited high transparency of over 70% in the visible-infrared range and a notable THz transmission of 64.5–73.9% at 0.1–1.5?THz. The VO₂ thin film was prepared on a transparent AlON ceramic using the sol-gel method and showed excellent optical and electric switching performance. The square resistance variance was close to four orders of magnitude, and an infrared switching ratio of over 40% was obtained. Furthermore, the combined structure showed an efficient THz switching ratio of approximately 70.9%. This study proposes a composite material combined with a transparent ceramic and a phase transition oxide and provides great insights into their application in infrared and terahertz smart windows as well as in switching devices.     

Shrinkage features,microstructure evolution and properties of Gd2O3-MgO optical composite ceramics with Zr as phase stabilizer

A novel composite ceramic, composed of equal-volumetric Zr-stabilized Gd₂O₃ and MgO phases, was prepared to be transparent in mid-wave infrared range. Zr stabilized Gd₂O₃ is proved to have a lower lattice parameter (10.7516 Å) using XRD refinement. Pressureless sintering behavior of Gd₂O₃-MgO with/without 2 at% Zr-doping (naming ZGM and GM) was studied via the real-time observation technique. The shrinkage of ZGM green body proceeds steadily up to 1400 °C while that of the undoped one shrinks sharply at 1250 °C due to Gd₂O₃ phase transition. The segregation of Zr element along the grain boundaries of Zr-Gd₂O₃ creates a synergized effect on the grain refinement with pinning effect. Dense ZGM ceramics exhibit superior transmittance of 78.3 %‐85.6 % at 3–5 µm, which show good consistency with the calculated values. The refractive index of Zr- Gd₂O₃ varies from 1.87 at 3 µm to 1.80 at 5 µm, which is smaller than those of monoclinic Gd₂O₃.     

Phase transition,microstructure, and dielectric properties of Li/Ta/Sb co-doped (K,Na)NbO3 lead-free ceramics

Li/Ta/Sb co-doped lead-free (K_0.4425Na_0.52Li_0.0375)(Nb_0.93−xTa_xSb_0.07)O₃ (abbreviated KNLNST_x) piezoelectric ceramics, with Ta-doping ratio of x ranging from 0.0275 to 0.0675, were synthesized using the conventional solid-state reaction method at the sintering temperature of 1130 °C. The effects of Ta content on the microstructure, dielectric properties, and phase transition behavior of the prepared ceramics were systematically investigated. The X-ray diffraction results show that all KNLNST_x ceramics formed a secondary phase, which is assigned to the tetragonal tungsten-bronze type (TTB) structure phase, and showed a phase transition from an orthorhombic symmetry to a tetragonal symmetry across a composition region of 0.0375<x<0.0475. The grain shape and size that correspond to the phase structure transformations can be clearly observed in the scanning electron microscopy images. As x increased to 0.0475, the KNLNST_0.0475 ceramics changed from orthorhombic to tetragonal structure and showed excellent piezoelectric properties of d₃₃=313 pC/N, k_p=47%, and ε_r=1825. By contrast, samples of x=0.0375 with orthorhombic symmetry exhibited poor piezoelectric properties, with d₃₃=200 pC/N and ε_r=1015. These results indicate that phase structure is vital in the piezoelectric properties of KNN lead-free ceramics.     

Morphotropic phase boundary and electrical properties of lead-free (K0.5Bi0.5)TiO3–Bi(Ni0.5Ti0.5)O3 relaxor ferroelectric ceramics

Lead-free relaxor ferroelectric ceramics (1?x)(K_0.5Bi_0.5)TiO₃–xBi(Ni_0.5Ti_0.5)O₃ were prepared by a conventional solid-state route, the phase transition behavior and corresponding electrical properties were investigated. A typical morphotropic phase boundary (MPB) between rhombohedral and tetragonal ferroelectric phases was identified to be in the range of 0.05<x<0.07 where the optimum piezoelectric and electromechanical properties of d₃₃=126 pC/N and k_P=18% were achieved. Most importantly, a high Curie temperature ~320 °C, around which the material shows a typical relaxor ferroelectric behavior characterized by the presence of diffuse phase transition and frequency dispersion, was obtained in MPB compositions, significantly higher than those of some existing MPB lead-free titanate systems. These results demonstrate a tremendous potential of the studied system for device applications.     

KNN–Eu transparent ferroelectrics: Local structure and luminescent property

Differ from the rapid development of piezoelectricity in potassium sodium niobate (KNN) ceramics, the progress of photoluminescence in transparent KNN ferroelectric ceramics remains stagnant. Herein, europium (Eu)-doped KNN ceramics have been prepared to investigate its local structure and optical–electrical multi-functionality. Both enhanced piezoelectricity in ceramics with a bimodal distribution of grain size and improved luminescent property in ceramics with refined grain size can be achieved by adjusting the content of Eu. The addition of Eu can destroy long-range ferroelectric orders, leading to the formation of pseudo-cubic phase and polar nanoregions (PNRs). The highly activated PNRs promoted electric field-induced domain switching and nearly reversible piezo/ferroelectric properties. First-principles calculations show that Eu substitution will lead to local inhomogeneous chemical bond environment, affecting the local electric/elastic fields and crystal fields, and then benefiting to the luminescence behavior, including both the intensity and lifetime. We believe that this work can benefit to the development of KNN transparent luminescent ceramics and the light-emitting devices.     

Fabrication of Transparent Grain‐Oriented Polycrystalline Alumina by Colloidal Processing

Grain‐oriented polycrystalline alumina (PCA) ceramics with very high, nearly single‐crystal transparency were successfully fabricated through colloidal processing in a high magnetic field followed by hot isostatic pressing. The c‐axis of the produced material was oriented along the direction parallel to the magnetic field. The transmittance of the specimen with a thickness of 0.8 mm was 78% at a wavelength of 650 nm, close to the reported value of 84.5% for sapphire and more than 10% higher than the largest transmittance magnitude ever reported for PCA ceramics. In addition, the Na salt of 4,5‐dihydroxy‐1,3‐benzenedisulfonic acid (named “Tiron”) was found to be a highly effective dispersant for processing high‐purity materials.