Structure,microstructure and electrical properties of Cu2+ doped (K,Na,Li)(Nb,Ta,Sb)O3 piezoelectric ceramics

This work studies the effects of copper doping on the properties of the (K_0.44Na_0.52Li_0.04)(Nb_0.86Ta_0.10Sb_0.04)O₃ piezoelectric ceramic material. Cu²⁺ incorporation into the perovskite structure produces a transformation of the crystalline lattice from tetragonal to orthorhombic symmetry together with an increase of the secondary phase. The grain size of the ceramic samples is increased due to the formation of a liquid phase during sintering, which increases with the Cu²⁺ content. EDS analysis reveals that the secondary-phase regions present a Cu and Nb-rich composition, indicating that the Cu-excess accommodates through the formation of this secondary phase. Cu-doping induces a rapid increase of the orthorhombic–tetragonal phase transition temperature, while the tetragonal–cubic phase transition temperature is decreased, the latter becoming more diffuse with the increase of Cu content. The piezoelectric properties of the material are reduced with the copper concentration, whereas the mechanical quality factor increases by a factor of nearly four.     

Laser welding of niobium to AISI 304 steel using a copper interlayer

Abstract

Cu interlayers with thicknesses of 1, 1.5, and 2?mm were used to join niobium and AISI 304 steel. Fractures occurred in the weld, the Nb base metal, and the unmelted Cu interlayer when the Cu interlayer thickness was 1, 1.5, and 2?mm, respectively. When the thickness of the Cu interlayer was 1?mm, the weld microstructure consisted of austenite with Cu-rich particles along the austenitic grain boundaries and within the austenitic grains, a composite-like structure (the Fe₂Nb lamellae and particles in a γ matrix) embedded with coarse Cu globules, and a mixture of bulk Fe₇Nb₆, Nb-rich dendrites, and Cu matrix. The bulk brittle Fe₇Nb₆ phase embrittled the joint. However, when the thickness of the Cu interlayer was 1.5?mm, the weld microstructure consisted of austenite with Cu-rich precipitates along the austenitic grain boundaries and a Cu-rich phase embedded with Nb-rich particles and dendrites. Solid-solution strengthening of Cu by Fe was responsible for the improved mechanical properties of the joint. The mixture of Nb-rich particles and dendrites in the Cu matrix was also helpful in enhancing the joint strength. Furthermore, when the thickness of the Cu interlayer was 2?mm, the weld microstructure consisted of austenite with Cu-rich precipitates along the austenitic grain boundaries and within the austenitic grains, an unmelted Cu interlayer, and Nb-rich particles and dendrites embedded in a Cu matrix. The unmelted Cu interlayer reduced the joint strength.     

Effect of tantalum solid solution additions on the mechanical behavior of ZrB2

Mechanical properties and microstructure were compared for zirconium diboride and two zirconium diboride solid solutions containing 3 and 6 at% tantalum diboride. X-ray diffraction indicated that the ceramics were nearly phase-pure and that tantalum dissolved into the ZrB₂ lattice to form (Zr,Ta)B₂ solid solutions. Microstructural analysis indicated that samples achieved nearly full relative density with average grain sizes that ranged from 3?5 μm. The three compositions had similar values of Young’s modulus (510?531 GPa), shear modulus (225?228 GPa), Vickers hardness (15.2–16.4 GPa), and flexural strength (391?452 MPa). Fracture toughness ranged from 2.6 to 3.7 MPa m^1/2 and with increasing tantalum content, the fracture mode changed from predominantly intergranular to predominantly transgranular. Diboride solid solution materials had comparable properties to the single metal diboride, but differences in microstructure, secondary phases, and strain state among the three ceramics partially obscured the actual effects of the solid solution on fracture behavior.     

Structural insights of mechanically induced aluminum-doped hydroxyapatite nanoparticles by Rietveld refinement

Aluminum doped hydroxyapatite(HA:Al~(3+)) nanopowders were successfully prepared via a simple and efficient one-pot mechanochemical route. The effects of dopant loading on phase compositions and structural features were assessed by Rietveld analysis. The XRD-Rietveld refinement revealed the stabilization of HA in hexagonal structure for all the samples. The sharpness and intensity of the apatite-derived XRD peaks decreased as the dopant content increased to 10% due to the increase in lattice imperfections and mechanically induced amorphization. The incorporation of Al3+into the HA lattice decreased the unit cell parameters. From the FTIR measurements, the representing bands of apatite were identified in all cases. The mechanosynthesized nanopowders consisted of nanospheroids with an average size of 44 ± 20 nm and therefore are promising for bone tissue regeneration.     

Processing of dense high-entropy boride ceramics

Dense (Hf_0.2,Zr_0.2,Ti_0.2,Ta_0.2,Nb_0.2)B₂ high-entropy ceramics with high phase purity were produced by two-step spark plasma sintering of precursor powders synthesized by boro/carbothermal reduction of oxides. The reacted powders had low oxygen (0.404 wt%) and carbon (0.034 wt%) contents and a sub-micron average particle size (∼0.3 μm). Powders were synthesized by optimizing the excess B₄C content of the reaction mixture and densified by a two-step spark plasma sintering process. The relative density increased from 98.9% to 99.9% as the final sintering temperature increased from 2000 °C to 2200 °C. The resulting ceramics were nominally single-phase (Hf,Zr,Ti,Ta,Nb)B₂ with oxygen contents as low as 0.004 wt% and carbon as low as 0.018 wt%. The average grain size increased from 2.3 ± 1.2 μm after densification at 2000 °C to 4.7 ± 1.8 μm after densification at 2100 °C, while significant grain growth occurred during sintering at 2200 °C. The high relative densities, low oxygen and carbon contents, and fine grain sizes achieved in the present study were attributed to the use of synthesized precursor powders with high purity and fine particle size, and the two-step synthesis-densification process. These are the first reported results for dense high-entropy boride ceramics with high purity and fine grain size.     

Increase of Mn solubility with decreasing grain size in ZnO

Nanograined (grain size 20 nm) ZnO films with various Mn content (from 0 to 47 at%) were synthesized by the novel wet chemistry method. The solubility limit for Mn was determined at 550 °C. The lattice parameter c of the ZnO-based solid solution with wurzite structure ceases to grow at 30 at% Mn. The peaks of the second phase (Mn₃O₄ with cubic lattice) become visible in the X-rays diffraction spectra at 30 at% Mn. The same second phase appears in the bulk ZnO already at 12 at% Mn. The recently published papers on the structure and magnetic behaviour of Mn-doped ZnO allowed us to obtain the size-dependence of Mn solubility in ZnO for the polycrystals and small single-crystalline particles. The overall Mn solubility drastically increases with decreasing grain size. The quantitative estimation leads to the conclusion that, close to the bulk solubility limit, the thickness of an Mn-enriched layer is several monolayers in GBs and at least two monolayers in the free surfaces.     

Ionic conductivity and relaxations of In-doped GDC (gadolinium doped ceria) ceramics

The effect of In doping on the sintering behaviors and electrical properties of Gd_0.1Ce_0.9O_1.95 (Gd-doped ceria, or GDC) was investigated. The solubility limit of In in GDC was determined to be ~2 at%, and the lattice parameter of GDC was found to decrease from 5.417(7) Å to 5.416(5) Å with 2 at% In dopant. The mean grain size of the sintered body decreased with increasing In content. The concentration of In did not significantly affect the conductivity of the samples; however, undoped GDC showed the highest conductivity. Cole-Cole plots showed that the activation energies of the grain boundaries and grain interiors decreased and increased, respectively, as the In concentration increased to 1 at%. The decreased grain-boundary activation energy is attributed to the segregation of the negatively charged dopant at the grain boundaries, while the increased activation energy of the grain interiors is attributed to the decreases in both the lattice parameters and binding energies with In doping.     

高效液相色谱法测定愈创木酚甘油醚、福尔可定和马来酸氯苯那敏含量

采用高效液相色谱法同时测定愈创木酚甘油醚、福尔可定和马来酸氯苯那敏的含量.色谱柱为C18 (4.6mm×250 mm,5 μm),流动相为0.05 mol·L-1磷酸二氢钾溶液(每1000 mL加庚烷磺酸钠4.0g、三乙胺1.0 mL,用磷酸调pH值至2.5)—乙腈—甲醇(50∶ 20∶ 30),流速为1.0 mL·m...     

Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

A method for the preparation of NiO and Nb–NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb–Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7–13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1–2 nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb₂O₆. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5 at.%, Nb–NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3–4 at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb–NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst.     

Higher permittivity of Ni-doped lead zirconate titanate,Pb[(Zr0.52Ti0.48)(1-x) Nix]O3, ceramics

The paper reports highest obtained dielectric constant for Ni-doped Lead Zirconate Titanate [PZT, Pb(Zr_0.52Ti_0.48)O₃] ceramics. The Ni-doped PZT ceramic pellets were prepared via conventional solid-state reaction method with Ni content chosen in the range 0–20?at%. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were employed to investigate the crystal structure of the prepared ceramics. The X-ray diffraction analysis indicated that the ceramic pellets had crystallized into tetragonal perovskite structure. A minute displacement of XRD peaks was detected in the diffraction spectra of Ni-doped PZT ceramic samples which when examined by size-strain plot (SSP) method revealed presence of homogenous strain that decreased with increase in concentration of Ni. In FTIR the maximum absorption at 597?cm^?1, 608?cm^?1, 611?cm^?1, 605 and 613?cm^?1 for Ni?=?0, 5, 10, 15 and 20?at%, respectively, confirmed the formation of perovskite structure in all the compositions and the slight shift suggests decrease in cell size on doping. The values of dielectric constant (ε′) & tanδ as a function of frequency and temperature were measured for the prepared ceramics and it revealed highest ever reported dielectric constant for Ni - doped PZT with Ni?=?5?at%. The dielectric variation with temperature exhibited a diffused type ferroelectric–paraelectric phase transition for the doped samples. Also, the maximum dielectric constant value (ε′_max) decreased while the phase transition temperature increased with increase in doping concentration of Ni. The estimated activation energy of different compositions was found to increase from 0.057 to 0.068?eV for x?=?0.00 to x?=?0.20 in ferroelectric phase. The piezoelectric, ferroelectric and magnetic properties were also investigated.     

Facile synthesis of highly uniform Mn/Co-codoped ZnO nanowires: optical, electrical, and magnetic properties

In this article, Co/Mn-codoped ZnO nanowires (NWs) were successfully synthesized on a silicon substrate by the thermal evaporation method with Au catalyst. The X-ray diffraction pattern indicated that the Co/Mn-codoped ZnO NWs are a hexagonal wurtzite structure without a second phase, and energy dispersive X-ray spectroscopy revealed that the Co and Mn ions were introduced into the ZnO NWs with the content of ～0.8 at% and ～1.2 at%, respectively. Photoluminescence spectra and Raman spectra showed that the Co/Mn were doped into the NWs and resulted in the shift of the near-band-edge emission. Moreover, the novel Raman peak at 519.3 cm(-1) has suggested that the two kinds of cations via doping could affect the local polarizability. Compared with the undoped ZnO NW, the electrical measurement showed that the Co/Mn-codoping enhanced the conductivity by an order of magnitude due to the presence of Co, Mn cations. The electron mobility and carrier concentration of a fabricated field effect transistor (FET) device is 679 cm2 V(-1) s(-1) and 2×10(18) cm(-3), respectively. Furthermore, the M-H curve demonstrated that the Co/Mn-codoped ZnO NWs have obvious ferromagnetic characteristics at room temperature. Our study enhances the understanding of the novel performances of transition-metal codoped ZnO NWs and also provides a potential way to fabricate optoelectronic devices.     

Optimising the performance of SiC-based varistors through composition and microstructure control

SiC varistors are employed as surge arrestors in high power/high energy niche applications. Using a model formulation based on 50 % SiC and 50 % clay plus graphite, the effects of SiC grain size, composition and graphite content were investigated. Disc and toroidal samples were sintered at 1130 °C under a reducing atmosphere; products were ～70–75 % dense. The main phases detected by SEM and XRD were SiC, SiO₂ (quartz), mullite, graphite and porosity. With increasing graphite content (zero to 11 wt%) the non-linear coefficient (α) decreased from 5.9 to 2.7, the breakdown field E_b decreased from 3346 to 36 V cm^?1, and bulk electrical resistivity fell by three orders of magnitude. As SiC grain size reduced from 120 μm to 10 μm, non-linear coefficients (α) almost doubled (3.7–6.3) and breakdown field (E_b) increased by an order of magnitude (226–2656 V cm^?1) as a result of increasing numbers of resistive grain boundaries between the device electrodes. The impurity content of SiC grains had a modest impact on electrical properties. The resistance of grain boundary regions was typically one to two orders of magnitude larger than that of grain cores.     

Transition of Compensating Defect Mode in Niobium-Doped Barium Titanate

The influence of Nb-doping from 1.0 to 8.0 at.% on grain size, ferroelectric phase transition, lattice strain, and electrical properties of BaTiO₃ Cerumics has been studied. A change in the Nb-doping effect was observed at compositions around 3.5–4.5 at.% Nb. The impedance behavior revealed that specimens of low Nb-doping had an activation energy of 1.85 eV for carrier conduction either in bulk or at grain boundaries, but specimens having a high Nb-doping content showed an energy of 1.30 eV in bulk and 1.85 eV at grain boundaries. The capacitance–voltage relation also disclosed different influences of Nb-doping on the potential barrier height at grain boundaries. The above results are explained by the transition of a compensating defect mode from pure barium vacancies to a combination of titanium vacancies in grain interiors and barium vacancies at grain boundaries as the Nb-doping content in BaTiO₃ is increased.     

正交法在PTA生产中粒径控制上的应用

介绍了正交试验法在PTA生产中粒径控制上的应用。对第一、二结晶器采用L9( 34)正交表进行试验 ,选出最优操作方案为第一结晶器液位为 2 6 %、压力为 3 6 0 0kPa ,第二结晶器液位为 45 .5 % ,压力为 2 40 0kPa ,结果是 :平均粒径从原来的 ( 118± 10 ) μm控制到 ( 118± 8) μm左右 ,粒径小于 45 μm的从原来的 2 0 %下降到 15 %左右 ,粒径 2 5 0 μm以下的由 93 %上升到95 %左右     

The role of Cr addition on the processing and mechanical properties of high entropy carbides

Group VI transition metals do not form room temperature stable carbides with a rock salt structure, however, they can be incorporated into a rock salt high entropy carbide lattice. Novel 5-metal high entropy carbides (Cr, Zr, Nb, Hf, Ta)C (HEC5-Cr) were produced using spark plasma sintering and compared with 4-metal carbide (Zr_0.25Nb_0.25Hf_0.25Ta_0.25)C (HEC4) and 8-metal carbide containing Cr (HEC8-Cr). The HEC5-Cr ceramics had higher density and smaller grain size (~14 µm) compared with HEC4 (~28 µm). The solubility limit of Cr on the metal site increased from ~2.5 at% for HEC5-Cr to ~6.0 at% for HEC8-Cr, implying that the high entropy effect increased the solubility of Cr. A significant Cr enrichment was observed at the grain boundaries of HEC5-Cr, and it showed a ~14% increase in nanohardness and a similar indentation modulus compared with HEC4. The nanohardness of HEC5-Cr was up to 41.2 GPa due to increased solid solution strengthening.     

Effect of Nb Doping on the Microstructure of Sol—Gel-Derived PZT Thin Films

Aliovalent Nb doping (<10 at.%) of sol—gel-derived lead zirconate titanate (PZT) thin films was investigated with the intention of improving the ferroelectric properties. Nb addition was found to significantly alter the perovskite crystallization by stabilizing the transient pyrochlore phase, resulting in the retention of pyrochlore second phases and an increase in the perovskite lateral grain size and columnarity. The occurrence and composition of Zr-rich (surface) pyrochlore phases were found to depend on Nb concentration, annealing temperature, and Pb content. The observed changes in ferroelectric and dielectric properties as a function of Nb dopant addition were found to be strongly influenced by microstructural effects and the occurrence of pyrochlore, and hence the intrinsic effects of Nb incorporation in the perovskite lattice could not be directly ascertained.     

The structural and mechanical characterization of TiC and TiC/Ti thin films grown by DC magnetron sputtering

The formation of TiC and Ti phases and their influence on their mechanical properties was studied in this work. Thin layers were deposited by DC magnetron sputtering at room temperature in ultrahigh vacuum from Ti and C targets.Cubic TiC phase (c-TiC) was formed from 58 to 86?at.% Ti content. First formation of hexagonal Ti (h-Ti) occurred from 86?at.% Ti content. The c-TiC disappears from 90?at.% Ti content. Films with 86?at.% Ti content the c-TiC structure can transform to h-Ti by sequential stacking faults. Dominance of c-TiC(111) texture with increasing Ti content was observed.The hardness of thin films agree with structural observations. The highest hardness value (～26?GPa) showed the c-TiC thin film with 67?at% Ti content. The nanohardness values showed decreasing character with increasing Ti content over 70?at.%. The lowest values of nanohardness (～10?GPa) was observed for thin films with only h-Ti phase.     

Ceramic TiC/a:C protective nanocomposite coatings: Structure and composition versus mechanical properties and tribology

The relationship between the structure, elemental composition, mechanical and tribological properties of TiC/amorphous carbon (TiC/a:C) nanocomposite thin films was investigated. TiC/a:C thin film of different compositions were sputtered by DC magnetron sputtering at room temperature. In order to prepare the thin films with various morphology only the sputtering power of Ti source was modified besides constant power of C source. The elemental composition of the deposited films and structural investigations confirmed the inverse changes of the a:C and titanium carbide (TiC) phases. The thickness of the amorphous carbon matrix decreased from 10 nm to 1–2 nm simultaneously with the increasing Ti content from 6 at% to 47 at%. The highest hardness (H) of ~26 GPa and modulus of elasticity (E) of ~220 GPa with friction coefficient of 0.268 was observed in case of the film prepared at ~38 at% Ti content which consisted of 4–10 nm width TiC columns separated by 2–3 nm thin a:C layers. The H3/E2 ratio was ~0.4 GPa that predicts high resistance to plastic deformation of the TiC based nanocomposites beside excellent wear-resistant properties (H/E=0.12).     

Addition of a Sr, K, Nb (SKN) Combination to PZT(53/47) for High Strain Applications

A lead zirconate titanate composition incorporating the dopants Sr, K, and Nb (SKN) in the specific ratio 4:1:3 has been studied. In principle, the SKN should act as a donor dopant but since its addition reduced the grain size from 11.4 μm (for 1% SKN) to 1.5 μm (for 5% SKN), the overall effect was found to be more complicated. It was observed that the addition of SKN reduced the Curie temperature, by 16°C/mol (%) and broadened the dielectric peak. X-ray measurements further suggested that the ceramic was a mixture of rhombohedral and tetragonal phases and that the room temperature c/a ratio of the tetragonal phase decreased with SKN addition. The piezoelectric coefficient d ₃₃, determined from high field unipolar drives, gave an optimum value of 779 pm/V for the 0.02 SKN compositions, which also exhibited a relatively high Curie temperature of 356°C. Competing effects of enhanced domain wall mobility from donor doping and reduced mobility due to smaller grain size may explain the observed compositional variation in the measured material properties. Materials based on this composition are attractive for high performance piezoelectric actuator applications such as fuel injection.     

Effect of carbon and tungsten content on the phase equilibria,microstructure, and mechanical properties of (Nb,W)C–Ni cermets

With the assistance of thermodynamic simulation, the NbC–Ni based cermets with different W and C additions were designed and sintered in liquid state at 1390°C for 90 min in vacuum. By controlling the carbon and tungsten content, (Nb,W)C–Ni based cermets were prepared with varied phase constitution, microstructure, and mechanical properties. The microstructure, composition of phases, grain size, and equilibrium phases were investigated using scanning electron microscopy, electron probe microanalysis, EBSD, and X-ray diffraction. The simulation reasonably predicted the experimentally observed phase constitutions. Depending on the additions, detailed analysis indicated that the cermets were composed of either a combination of cubic (Nb,W)C solid solution and Ni alloy binder or with an additional carbon-deficient phase. Furthermore, mechanical analysis showed a strong dependence of its mechanical properties (Vickers hardness, indentation toughness, and flexural strength) on the phases and NbC grain size.