Contribution of some transition metal oxides to crystallization and electro-thermal properties of glass-ceramics

Lithium di-silicate (LS₂) glass-ceramics modified with copper oxide using the formula: 34.83Li₂O–xCuO–(65.17-x)SiO₂ (where; x = 1, 2, 4 and 6 mol%) were prepared by melt-quenching followed by controlling heat-treatment. 6 mol% of MnO or Fe₂O₃ transition metal oxides was added instead of SiO₂ in the high CuO-content composition. The effect of the transition cations on phase formation, microstructure, density, thermal expansion, and electrical conductivity was investigated as a function of the controlled crystallization. Results show that up to 4 mol%, Cu⁺² was hosted in stable Li₂Si₂O₅ structure. This enhanced the crystal formation, including Li₂Si₂O₅ and its solid solution (ss), Li₂SiO₃, Li₂Cu₅(Si₂O₇)₂, CuMn₆SiO₁₂, LiFeSi₂O₆ (ss), and the orthosilicate Li₂FeSiO₄ (ss). The prepared materials had different density values ranged from 2.35 to 2.79 g/cm³ for glass and varied from 2.43 to 3.15 g/cm³ for glass–ceramics, whereas the α-values of glass-ceramics ranged in the 95–165 × 10⁻⁷/°C. The progress of electrical properties in glass-ceramics, as a function of composition, was studied. It was markedly improved by adding different transition cations especially, Fe⁺³. The study reveals that the incorporation of transition metal ions in LS₂ composition has a positive effect on the physical-chemical properties of the prepared glass-ceramics. Therefore, it constitutes to prepare future glass-ceramic applications as hermetic seals of metals as well solid electrolyte materials.     

Simultaneous tuning of the phase transition temperature and infrared optical properties of Mo-doped VO2 powders for intelligent infrared stealth materials

The development of an intelligent infrared camouflage material whose infrared emissivity can actively adapt to environmental changes is a key frontier in the field of infrared stealth. In this study, Mo-doped VO₂ powder was prepared via a hydrothermal method, which led to an intelligent infrared camouflage material whose infrared radiation characteristic can adaptively change with the environmental temperature. The samples were characterized by XRD, SEM, DSC, FTIR and infrared thermal imaging. Combined with the results of the first-principles calculation, the coupling effect mechanism of Mo⁶⁺ doping concentration on the phase transition temperature and infrared photoelectric properties of VO₂ material was systematically analyzed. The results showed that Mo⁶⁺ impurities had significant effects on the structure, morphology, composition, phase transition temperature and infrared reflectivity of VO₂ powder. The doping process effectively reduced the phase transition temperature of VO₂ and expanded the change range of infrared emissivity (△ε) before and after the metal-to-insulator (MIT) transition. With the increasing amount of Mo⁶⁺ doping, the infrared reflectance of VO₂(M) gradually decreased at low temperatures, while the infrared reflectance of VO₂(R) increased at high temperatures. The MIT transition temperature of Mo-doped VO₂ versus undoped VO₂ reduced to 31.5 °C, and the △ε increased by 153%, this is expected to meet the performance requirements of intelligent infrared stealth materials.     

Mechanical properties study of VO2 micro-beam according to metal-insulator transition

Many attempts have been made to develop applications using the metal-insulator transition (MIT) phenomenon of VO₂. However, the difference in the densities of the two phases poses serious obstacle for those applications, as it can destroy or disable during the phase transformations. For microsized or nanosized devices, this aspect can be critical. We attempted to measure the mechanical properties when the two phases co-exist, as well as for an individual phase, via in-situ control of the temperature of plate-shaped VO₂. The lamella structure is formed during MIT. At this time, the stress is applied by the gradient of density, and the residual strain can easily occur at the interface of each phase. Therefore, the co-exist state was judged to be the most vulnerable during the MIT. The change in mechanical properties of VO₂ during phase transition was also simulated by finite element method.     

Ferroelectric phase transition and electrical conduction mechanisms in high Curie-temperature PMN-PHT piezoelectric ceramics

Ferroelectric phase transition characteristic and electrical conduction mechanism of the high Curie-point (T_C) 0.15Pb(Mg_1/3Nb_2/3)O₃−0.4PbHfO₃−0.45PbTiO₃ (PMN-PHT) piezoelectric ceramics were studied by the temperature dependent Raman spectra and electrical properties. Sole first-order ferroelectric phase transition is demonstrated by the thermal hysteresis behavior of the temperature dependent dielectric constant and the dramatic drop of the derivative of inverse dielectric constant ξ= d(1/ε_r)/dT around T_C in the PMN-PHT ceramics. The temperature dependent Raman spectroscopy not only provides further evidence for the ferroelectric to paraelectric phase transition appearing around T_C in the PMN-PHT ceramics, but also reveals the successive phase symmetry changes of the polar nanoregions (PNRs), in which apparent anomalies appear in the Raman peaks' wavenumber, wavenumber distance, intensity, intensity ratio, and line width of some selected Raman modes upon heating. Typical sole cole-cole circle is obtained for the PMN-PHT ceramics in the temperature range of 440–560 °C, based on which the activation energy (E_a) of the electrical conduction is calculated being ~1.2 eV. Such low value of E_a indicates that the oxygen vacancies formed in the PHT-PMN ceramics induced by the evaporation of Pb during the sintering process dominate the high-temperature extrinsic electrical conduction.     

Controlling metal-insulator transition in (010)-VO2/(0001)-Al2O3 epitaxial thin film through surface morphological engineering

Surface morphological control of the metal-insulator transition behaviors of VO₂ epitaxial thin films is achieved by annealing substrates of (0001)-Al₂O₃ single crystals. The well-defined terraces of the (0001)-Al₂O₃ substrates are formed by annealing in air at 1200 °C. Correspondingly, the surface roughness dramatically decreases in the VO₂ epitaxial thin films on the annealed substrates, compared with that on the unannealed substrates. The order of magnitude of the resistivity change ratio (~ 10²) of annealed samples across the metal-insulator transition (MIT) decreases by a factor of one, compared with that (~ 10³) in unannealed samples. This result is ascribed to grain size effect in the VO₂ epitaxial thin films. Moreover, the MIT temperature is reduced in the annealed samples with various thickness, compared with the unannealed ones. A reduction of 14.4 K of the MIT temperature is observed in the thinnest VO₂ films on the annealed substrates, compared with the unannealed samples. This behavior results from a compressive strain along the V-V atom chains in the annealed samples, which modifies the orbital occupancy of the V⁴⁺ ions. While increasing the film thickness, the MIT change ratio keeps on the order of magnitude 10², and the MIT temperatures of the VO₂ films on the annealed substrates becomes closer and closer to those of the unannealed samples due to the weakened substrate effect. This work suggests a promising approach to decrease the MIT temperature and still maintain a moderate change ratio for the MIT, potentially enabling room-temperature electronic devices based on VO₂ thin films.     

过渡金属氮化物催化性能研究进展

过渡金属氮化物具有类似于Pt族贵金属的催化性能得到了广泛的研究.综述了过渡金属氮化钼及助剂促进的氮化钼在加氢脱硫与脱氮、氨合成与分解、芳烃加氢和其他涉氢反应(如炔烃、烯烃加氢、丙酮缩合、肼的分解)中的应用,并介绍了其他金属氮化物(如氮化钒、氮化钴)在催化反应中的应用.     

The effect of particle size on structural,magnetic and transport properties of La0.7Sr0.3MnO3 nanoparticles

This paper reports the synthesis of different particle size La_0.7Sr_0.3MnO₃ (LSMO) nanoparticles using non-aqueous sol gel synthesis route by calcination at temperatures 750 °C, 850 °C and 950 °C. In the present work, the effect of particle size of LSMO nanoparticles on its structural, magnetic and transport properties has been studied in detail. The X-ray diffraction analysis confirms the formation of LSMO nanoparticles having rhombohedral ($R\stackrel{?}{3}c$) structure with average particle size of 20 nm, 22.5 nm and 25.6 nm. An increase in magnetization and decrease in coercivity with increase in particle size is attributed to the magnetically disordered surface layer. The bifurcation in ZFC-FC magnetization indicates the possibility of spin glass like behavior of the LSMO nanoparticles. The effect of particle size on the resistivity and magnetoresistance were studied by using different conduction mechanism for different temperature regions. The upturn in the ρ-T curve at lower temperatures was explained by using Kondo-like transport mechanism. The maximum LFMR achieved was 32.3% at a field of 1 T at 10 K for 20 nm LSMO nanoparticle.     

异羟肟酸过渡金属络合物在乙苯氧化中的催化性能研究

研究了 N-苯甲酰 -N-苯基羟胺 ( BPHA)类过渡金属络合物在乙苯均相氧化中的催化行为 ,考察了络合物催化剂中心金属离子、配体结构以及添加助剂对络合物催化性能的影响 ,并找到了催化剂、助剂的最佳使用浓度及氧化反应的最适宜温度。结果表明 ,中心金属离子的电子结构对络合物催化性能影响最大 ,其活性顺序为 :Cu( BPHA) 2 >Co( BPHA) 2 >Fe( BPHA) 2>Mn( BPHA) 2 >Ni( BPHA) 2 ,配体结构对催化性能有一定影响 ,配体的芳环上有吸电子基团时 ,催化剂分解氢过氧化物的能力增加 ,主要分解产物为苯乙酮。添加轴配体对氧化反应及催化剂的选择性有较大影响 ,其中含端羟基的非环冠醚类及大环冠醚对氢过氧化物的生成和分解都有加速作用 ,含氮助剂吡啶对氧化反应有抑制作用     

Semiconducting properties of cold sintered V2O5 ceramics and Co-sintered V2O5-PEDOT:PSS composites

Recently we established a sintering approach, namely Cold Sintering Process (CSP), to densify ceramics and ceramic-polymer composites at extraordinarily low temperatures. In this work, the microstructures and semiconducting properties of V₂O₅ ceramic and (1-x)V₂O₅-xPEDOT:PSS composites cold sintered at 120 °C were investigated. The electrical conductivity (25 °C), activation energy (25 °C), and Seebeck coefficient (50 °C) of V₂O₅ are 4.8 × 10⁻⁴ S/cm, 0.25 eV, and −990 μV/K, respectively. The conduction mechanism was studied using a hopping model. A reversible metal-insulator transition (MIT) was observed with V₂O₅ samples exposed to a N₂ atmosphere, whereas in a vacuum atmosphere, no obvious MIT could be detected. With the addition of 1–2 Vol% PEDOT:PSS, the electrical conductivity (50 °C) dramatically increases from 10⁻⁴ to 10⁻³ ∼ 10⁻² S/cm, and the Seebeck coefficient (50 °C) shifts from −990 to −(600 ∼ 250) μV/K. All the results indicate that CSP may offer a new processing route for the semiconductor electroceramic development without a compromise to the all-important electrical properties.     

Statistical mechanical theories of the glass transition — a new perspective

The statistical mechanical functions of Gibbs and DiMarzio are briefly reviewed, and subsequent modifications of these equations by other workers are described. Then using computer analysis, three-dimensional representations of the two original expressions are developed to illustrate the overall multifunctional dependence. By recognizing that the free volume (V₀) is of secondary importance but that the ratio of the dimensionless parameter ($\text{β = ?}\text{ε}\text{k}\text{T}{}_{\mathrm{g}}$) is crucial, a reduced variables plot of $\text{T}{}_{\mathrm{g}}\text{T}{}_{\mathrm{g\infty }}$ versus $\text{10}{}^3\text{P}\text{?}$ is introduced. From a representative data sampling, the applicability of a single curvilinear function is established along with some initial observations.     

First-principles investigation of elastic and electronic properties of double transition metal carbide MXenes

We use first-principles-based density functional theory (DFT) calculations to investigate the structural, elastic, and electronic properties of various pristine and oxygen (O)-functionalized double transition metal (DTM) MXenes with general formulas of M₂′M′′C₂ and M₂′M′′C₂O₂, where M′ = Mo, Cr and M′′ = Ti, V, Nb, Ta. The dynamic stability of the DTM MXenes are assessed and elastic stiffness constants (C_ij) are used to investigate the mechanical stability and properties of the compositions. The calculated elastic properties of the pristine Mo-based MXenes are found to be superior compared to Cr-based compounds. Furthermore, the O-functionalized MXenes exhibit improved in-plane elastic constants, Young's moduli, and shear moduli compared to their pristine counterpart. We observe that the hybridization of the energy states results in stronger covalent interactions as such increased elastic properties for the M₂′M′′C₂O₂ MXenes. Ashby plot clearly demonstrates superior materials properties of O-functionalized Mo-based DTM MXenes compared to other commonly known two-dimensional materials. All the MXenes exhibit metallic character evident from the density of states (DOS) calculations. Additionally, the work functions are studied and the calculated values are higher in the case of O-functionalized MXenes. Overall, this work will be a guide for future investigations on the mechanical properties of DTM MXenes for their targeted applications in structural nanocomposites.     

Ferroelectric phase transition and electrical properties of high-TC PMN-PH-PT ceramics prepared by partial oxalate route

The high-Curie temperature (T_C) 0.15Pb(Mg_1/3Nb_2/3)O₃-0.38PbHfO₃-0.47PbTiO₃ (PMN-PH-PT) piezoelectric ceramics were prepared by the partial oxalate route via the B-site oxide mixing method. The obtained uniform nm-sized PMN-PH-PT precursor powders provide high calcining and sintering activity for synthesizing ceramics, based on which the synthesis conditions were tailored as calcining at 775 °C and sintering at 1245 °C. The partial oxalate route synthesized PMN-PH-PT ceramics are far superior to the counterparts synthesized by the columbite precursor method and exhibit excellent thermal stability of the piezoelectric properties under T_C (～292 °C), ensuring the potential application in transducers under elevated environmental temperatures. The temperature dependent Raman spectroscopy not only proves the occurrence of the ferroelectric to paraelectric phase transition around T_C, but also confirms the successive phase symmetry transitions, which correlate with the polar nanoregions (PNRs) and/or the coexistence of multiple ferroelectric phases, revealing the origin of the enhanced electrical properties in the PMN-PH-PT ceramics.     

Effect of transition metal doping on the sintering and electrochemical properties of GDC buffer layer in SOFCs

A dense Ce_0.9Gd_0.1O_2−d (GDC) interlayer is an essential component of the SOFCs to inhibit interfacial elemental diffusion between zirconia-based electrolytes (eg YSZ) and cathodes. However, the characteristic high sintering temperature of GDC (>1400°C) makes it challenging to fabricate an effective highly dense interlayer owing to the formation of more resistive (Zr,Ce)O₂ interfacial solid solutions with YSZ at those temperatures. To fabricate a useful GDC interlayer, we studied the influence of transition metal (TM) (Co, Cu, Fe, Mn, & Zn) doping on the sintering and electrochemical properties of GDC. Dilatometry data showed dramatic drops in the necking and final sintering temperatures for the TM-doped GDCs, improving the densification of the GDC in the order of Fe > Co > Mn > Cu > Zn. However, the electrochemical impedance data showed that among various transition metal dopants, Mn doping resulted in the best electrochemical properties. Anode supported SOFCs with Mn-doped, nano, and commercial-micron GDC interlayers were compared with regard to their performance and stability levels. Although all of the SOFCs showed stable performance, the SOFC with the Mn-doped GDC interlayer showed the highest power density of 1.14 W cm⁻² at 750°C. Hence, Mn-doped GDC is suggested for application as an effective diffusion barrier layer in SOFCs.     

Shear properties of polystyrenes in the transition region

Shear properties of commercially available polystyrenes with narrow molecular weight distribution have been measured in the transition region from 100°C to 150°C and over a frequency range from 50 Hz to 1000 Hz. The effect of molecular weight or shear properties is established with four polymers ranging in molecular weight from 20,000 to 860,000. A broad, bimodal distribution is also studied. The properties of these polymers, with two different diluents added, illustrate the rather marked qualitative difference in effects caused by diluents.     

介孔过渡金属氧化物的合成研究进展

介孔过渡金属氧化物作为一种非硅基介孔材料,在光、电、磁、传感、催化等领域有着潜在的应用价值,是近年来研究的热点。本文主要从合成角度对几种典型的介孔过渡金属氧化物的最新研究进展作了总结,其中包括Ti、W、Nb、Mn、Mo、Ni、Co等。详细阐述了其合成方法、合成过程,也涉及了少量的应用研究,并根据目前合成该类材料所面临的难题,提出了介孔过渡金属氧化物以后的研究方向,即合成具有高热稳定性、孔壁高度结晶以及长程有序的介孔材料。     

Influence of plasticizers (DOP and CNSL) on mechanical and electrical properties of SBS/polyaniline blends

Electrically conductive blends based on polyaniline-dodecylbenzene sulfonic acid (Pani.DBSA)/styrene-butadiene-styrene (SBS) block copolymer have been prepared in the presence of different plasticizers such as dioctyl phthalate (DOP) and cashew nut shell liquid (CNSL). The products were characterized by ultraviolet-visible (UV-vis) spectrometry, scanning electron microscopy, X-ray diffraction, electron paramagnetic resonance (EPR) and resistivity measurements. The presence of DOP resulted in an increase of the electrical resistivity whereas the increasing concentration of CNSL resulted in a decrease of electrical resistivity. In the latter case, the presence of cardanol, a phenol-type compound in CNSL, may be responsible for the improved electrical performance, probably because of a secondary doping process, which changes the molecular conformation of Pani.DBSA chains from “compact coil” to “expanded coil”. In addition, CNSL contributes to the formation of cocontinuous-type morphology with conducting pathways in larger extension. EPR studies also showed an increase of the polaron mobility as the amount of CNSL in the blend increases.     

过渡金属羰基络合催化剂在有机合成中的应用及催化机理

过渡金属羰基络合物作为一种绿色、高效催化剂,在羰基化反应过程中起到了很好的催化作用。综述了几种主要的过渡金属羰基络合催化剂在羰基化反应中的主要应用及其催化机理。羰基化反应主要包括不饱和烃、有机卤代物、醇、杂环化合物等有机物的羰基化反应。     

Liquid-liquid phase transition and glass transition in a monoatomic model system

We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.     

Phase transition,microstructure and electrical properties of Fe doped Ba0.70Ca0.30TiO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics of Ba_0.70Ca_0.30Ti_1?xFe_xO₃ (x=0–0.03) have been synthesized by a conventional solid state reaction method. The influence of Fe content on the microstructure, phase transition, dielectric, ferroelectric, and piezoelectric properties is investigated systematically. The ceramics with x≤0.02 are diphasic composites of tetragonal Ba_0.80Ca_0.20TiO₃:Fe and orthorhombic Ba_0.07Ca_0.93TiO₃:Fe solid solutions. The tetragonal phase is gradually suppressed as x increases, the ceramic with x=0.03 is found to have diphasic pseudocubic and orthorhombic phases. And the grain size is dependent on Fe content significantly. Introduction of Fe at B-sites improves the densification and decreases the sintering temperature. As x increases from 0 to 0.03, the room temperature relative dielectric permittivity enhances, dielectric loss decreases, and the Curie temperature decreases monotonically from 128 °C to 58 °C. However, the ferroelectricity enhances slightly and reaches the maximum near x=0.005, and then weakens with increasing x. On the other hand, the piezoelectric coefficient (d₃₃) and the electromechanical coupling coefficient (k_p) decrease simultaneously with increasing x, whereas the mechanical quality factor (Q_m) increases significantly. The structure–electrical properties relationship is discussed intensively to give more information on (Ba,Ca)TiO₃-based lead-free piezoelectric ceramics.     

Role of Cu and Y in sintering,phase transition,and electrical properties of BCZT lead-free piezoceramics

Lead-free (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃-xwt%CuOywt%Y₂O₃ (BCZT-Cu_xY_y) ceramics with high piezoelectricity were synthesized by the conventional solid-state reaction method. The role of Cu and Y (Cu/Y) in sintering, phase transition, and electrical properties of such ceramics was systematically studied. The results indicated that the sintering temperatures of BCZT-Cu_xY_y decreased by at least 100?°C due to the low melting point of CuO. The promotion effect of Cu/Y on phase transition lied in the improvement of T_C by 5–15?°C and the coexistence of O+T phase near room temperature. The contribution of Cu/Y to electrical properties was mainly ascribed to the grains growth, the formed oxygen vacancies and lattice distortions, and the donor doping effect of Y³⁺. Adding 0.10?wt% Cu²⁺ and 0.06?wt% Y³⁺ into BCZT dramatically improved the electrical properties as following: d₃₃ =?552 pC/N, ε_m =?10175, ε_r =?4546, tanδ =?0.016, T_C =?100?°C, k_p =?0.475, Q_m =?157.2, P_r =?10.82 μC/cm² and E_C =?2.33?kV/cm. A plausible mechanism was obtained to explain the reaction process and the favorable performances of BCZT-Cu_xY_y. Co-doping Cu²⁺ and Y³⁺ into BCZT could be a promising method to improve and balance the sintering, phase transition, and electrical properties for potential practical applications of lead-free piezoceramics.