Comparison of corrosion behavior of zirconium bombarded with self-ion and molybdenum ion

In order to study the effects of zirconium and molybdenum ion bombardment on the aqueous corrosion behavior of zirconium, one group of specimens was implanted with zirconium ions with ions surface densities ranging from 1 × 10¹⁵ to 2 × 10¹⁷ ions/cm² at about 170 °C, using a metal vapor vacuum arc (MEVVA) source operated at an extraction voltage of 50 kV. The other group of specimens was bombarded with molybdenum ion with ions surface densities ranging from 1 × 10¹⁶ to 5 × 10¹⁷ ions/cm² at about 160 °C, using a MEVVA source operated at an extraction voltage of 40 kV. The valence states and depth distribution of elements in the surface of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Polarization curves measurement was employed to evaluate the aqueous corrosion resistance of the zirconium samples in a 1N H₂SO₄ solution. It was found that the aqueous corrosion resistance of zirconium implanted with 5 × 10¹⁶ Zr ions/cm² is the best in first group samples. For molybdenum ion implantation, the aqueous corrosion resistance of samples declined with raising ions surface densities. The natural corrosion potentials of zirconium samples bombarded with self-ions are more negative than that of the as-received zirconium. While, as for molybdenum ion implantation, the results are opposite. Finally, the mechanisms of the corrosion behavior of the zirconium samples implanted with zirconium and molybdenum ions are discussed.     

Framework flexibility of sodium zirconium phosphate: role of disorder, and polyhedral distortions from Monte Carlo investigation

A detailed Monte Carlo investigation of the structural changes of the framework of sodium zirconium phosphate, [Zr₂P₃O₁₂]⁻,—NASICON (acronym for Na-SuperIonic CONductor)—accommodating alkali ions of varying sizes (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) is carried out over a range of temperatures. Simulation results are critically compared with the structural models proposed earlier and available experimental results. Anisotropic changes of the rhombohedral cell parameters—a contracts while c expands with the size of the alkali ion substituted—is observed in good agreement with previous experimental results. The mechanism of anisotropic variation of lattice parameters involves dominantly, coupled rotations of the polyhedra as proposed by Alamo and co-workers. It is, however, observed that the distortions of the PO₄ tetrahedra and ZrO₆ octahedra are significant, and accounts for nearly one-third of the total change in a and c—parameters as the size of the alkali ion increases. This suggests that ‘rigid’ polyhedral models, permitting only angular distortions of the polyhedra, are of limited quantitative applicability in these solids. The same mechanism is found to be responsible for the low/anisotropic thermal expansion of these solids. Evidence that the polyhedral rotations are dynamic, opposed to a static-frozen-in disorder, is provided.     

Structural investigations of NASICON (Na1+xZr2SixP3−xO12; x=3) with x-ray diffraction at 298K and 403K

Structure investigations on the pure Si end phase of NASICON (Na_1+xZr₂Si_xP_3?xO₁₂; x=3) yielded an underoccupation of the Zr-site. The charge is not balanced by additional Na ions because all regular Na sites are nearly fully occupied and no additional Na site has been found. Infrared spectra show O-H defects in the structure. It is assumed that these defects can balance the charge. The thermal vibrations of the Na sites are both anisotropic and largely temperature dependent with anharmonic contributions at high temperature.     

Synthesis of sodium dizirconium triphosphate from α-zirconium phosphate

Heating sodium ion exchanged zirconium phosphates, ZrNa_xH_2?x(PO₄)₂, yields mixtures of phases which include NaZr₂(PO₄)₃. When x is less than one, the second phase is ZrP₂O₇. At values of x > 1 the products are Zr(NaPO₄)₂, NaZr₂(PO₄)₃ and possibly NaPO₃ + Na₂O. At x = 1 the products are NaZr₂(PO₄)₃ + NaPO₃. Hydrothermal treatment of ZrNa_xH_2?x(PO₄)₂ also yields triphosphates which contain some protons and zeolitic water. Zirconium phosphate treated hydrothermally in the presence of sodium silicates yields sodium zirconium silicophosphates.     

Full Activation of Mn4+/Mn3+ Redox in Na4MnCr(PO4)3 as a High‐Voltage and High‐Rate Cathode Material for Sodium‐Ion Batteries

Developing high‐voltage cathode materials is critical for sodium‐ion batteries to boost energy density. NASICON (Na super‐ionic conductor)‐structured Na_xMnM(PO₄)₃ materials (M represents transition metal) have drawn increasing attention due to their features of robust crystal framework, low cost, as well as high voltage based on Mn⁴⁺/Mn³⁺ and Mn³⁺/Mn²⁺ redox couples. However, full activation of Mn⁴⁺/Mn³⁺ redox couple within NASICON framework is still a great challenge. Herein, a novel NASICON‐type Na₄MnCr(PO₄)₃ material with highly reversible Mn⁴⁺/Mn³⁺ redox reaction is discovered. It proceeds a two‐step reaction with voltage platforms centered at 4.15 and 3.52 V versus Na⁺/Na, delivering a capacity of 108.4 mA h g^?1. The Na₄MnCr(PO₄)₃ cathode also exhibits long durability over 500 cycles and impressive rate capability up to 10 C. The galvanostatic intermittent titration technique (GITT) test shows fast Na diffusivity which is further verified by density functional theory calculations. The high electrochemical activity derives from the 3D robust framework structure, fast kinetics, and pseudocapacitive contribution. The sodium storage mechanism of the Na₄MnCr(PO₄)₃ cathode is deeply studied by ex situ X‐ray diffraction (XRD) and ex situ X‐ray photoelectron spectroscopy (XPS), revealing that both solid‐solution and two‐phase reactions are involved in the Na⁺ ions extraction/insertion process.     

Phase transitions and ionic mobility in hydrogen zirconium phosphates with the NASICON structure, H1±XZr2−XMX(PO4)3·H2O, M = Nb, Y

Phase transitions and the mobility of proton-containing groups in hydrogen zirconium phosphate HZr₂(PO₄)₃·nH₂O with the NASICON structure were studied by X-ray powder diffraction, ¹H, ³¹P NMR, IR spectroscopy and TG analysis. Heating HZr₂(PO₄)₃·H₂O above 420 K results in dehydration and in a rhombohedral-triclinic phase transition. Continued heating to about 490 K results in the thermal activation of cation disordering and phase transition of HZr₂(PO₄)₃ from triclinic to rhombohedral phase. Parameter “a” of HZr₂(PO₄)₃ lattice decreases during the heating. It is shown that oxonium ions in HZr₂(PO₄)₃·H₂O are characterized by high rotation and translation mobility. Rotation mobility of oxonium ions can be increased by the substitution of zirconium by yttrium or niobium.     

Effect of combined doping (y<Superscript>3 +</Superscript> + fe<Superscript>3 +</Superscript>) on structural features of nanodispersed zirconium oxide

Fully stabilized zirconium dioxide is widely used. One of the basic requirements to this material is the thermal stability of the structure. The most effective stabilizer for zirconium oxide is yttrium oxide. However, the structure of Y-ZrO₂ degraded at low temperature. Partial substitution of Fe^{3 +} for Y³⁺ decreases both the crystallization and sintering temperature of zirconia ceramic. The aim of present work is the investigation of structural peculiarities of zirconium oxide stabilized by combined dopant depending on chemical composition, synthesis conditions and heat treatment. The polymorphic composition of a ZrO₂-based materials has been determined in series of samples that correspond to the formula [1−(x+y)]ZrO₂⋅xY₂O₃⋅yFe₂O₃ in the temperature range 620–1570 K. It has been found that at the same molar ratio ZrO₂ : doping oxides, the degree of ZrO₂ stabilization increases, and the low-temperature degradation process is retarded by the partial substitution of Fe^{3 +} for Y³⁺. Nonequivalent sites of Fe^{3 +} ions have been identified: two with octahedral coordination for CPH and three with octa-, penta- and tetrahedral coordination for SPH. The possibility of cluster distribution of Fe³⁺ ions and the dependence of the number of vacancies on synthesis conditions have been shown.     

Influence of aluminum ions implanted on corrosion behavior of zirconium in 1 M H2SO4

In order to study the effect of aluminum ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with aluminum ions with fluence ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source (MEVVA) at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES), respectively. Transmission electron microscopy (TEM) was used to examine the microstructure of the aluminum-implanted samples. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the aluminum ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zirconium in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zirconium implanted with aluminum ions. Finally, the mechanism of the corrosion behavior of aluminum-implanted zirconium was discussed.     

Preparation of sodium zirconium phosphates of the type Na1+4xZr2−x (PO4)3

Sodium zirconium phosphates of the type Na_1+4x Zr_2?x (PO₄)₃ were prepared from mixtures of Na₃PO₄-ZrO₂-ZrP₂O₇ in sealed platinum tubes at temperatures of 900 – 1200°C. Stoichiometric NaZr₂ (PO₄)₃ (x = 0) was found not to exist. Instead, a solid solution in the range x = 0.02 ? 0.06 was found, with a slight difference in unit cell dimensions obtained. A second solid solution region was found with x = 0.88 – 0.93. At still higher values of x, a stoichiometric phase with hexagonal unit cell dimensions of $\text{a}\text{= 9.152(1)}\text{A}\text{?}$ and $\text{c}\text{= 21.844(1)}\text{A}\text{?}$ was obtained. Finally a phase of composition Na₇Zr_0.5 (PO₄)₃ was synthesized at the highest values of x. Attempts to prepare Na_5+x ZrSi_x-P_3?xO₁₂ always yielded NASICON and Na₇Zr_0.5 (PO₄)₃.     

Photoluminescence characteristics of NASICON materials

Besides gas sensitivity, luminescence characteristics of NASICON (Na⁺ super ion conductor) materials were found. In this paper, the photoluminescence (PL) properties of NASICON and doped-NASICON materials were investigated. NASICON was synthesized by conventional sol–gel process and doped with Dy₂O₃ by 1 wt.%, 3 wt.% and 5 wt.%, respectively. The ultraviolet light (325 nm, He–Cd laser) excited luminescent emissions of the resulted powders are recorded vs. wavelength in the range from 350 to 650 nm. The main peak of the pure NASICON is found at the wavelength of 474 nm (blue light), the transition energy is 2.616 eV. The luminescent intensity is increased after doping with Dy₂O₃.     

Pulsed laser annealing of sodium super ionic conductor for carbon dioxide sensors

This paper discussed a way to improve solid electrolyte carbon dioxide (CO₂) sensor by excimer laser annealing of sodium super ionic conductors (NASICON). The CO₂ sensor used in this paper consists of a thin NASICON layer. We additionally annealed the NASICON to improve its electrical conductivity by pulsed excimer laser. The laser annealing results in re-crystallization of the NASICON thin film and changes the conductivity, grain sizes, and the structure of grain boundaries. From the scanning electron microscope pictures, we saw that NASICON grain sizes were enlarged after laser annealing. Grain sizes were also correlated to laser annealing energy and annealing times. After 2 times annealing of 420 mJ laser energy with 7 pulses each time at 1 Hz repetition rate, the conductivity of NASICON was increased by 90%. When the CO₂ concentration was changed from 1000 ppm to 5000 ppm, the sensor resolution was enhanced up to 66%. These results suggested that appropriate laser annealing treatment not only enlarges NASICON grain sizes but also reduces its resistance. Therefore, the NASICON CO₂ sensor resolution can be improved accordingly.     

KTi2(PO4)3 Electrode with a Long Cycling Stability for Potassium‐Ion Batteries

In this work, rhombohedral KTi₂(PO₄)₃ is introduced to investigate the related theoretical, structural, and electrochemical properties in K cells. The suggested KTi₂(PO₄)₃ modified by electro‐conducting carbon brings about a flat voltage profile at ≈1.6 V, providing a large capacity of 126 mAh (g‐phosphate)^?1, corresponding to 98.5% of the theoretical capacity, with 89% capacity retention for 500 cycles. Structural analyses using electrochemical performance measurements, first‐principles calculations, ex situ X‐ray absorption spectroscopy, and operando X‐ray diffraction provide new insights into the reaction mechanism controlling the (de)intercalation of potassium ions into the host KTi₂(PO₄)₃ structure. It is observed that a biphasic redox process by Ti^4+/3+ occurs upon discharge, whereas a single‐phase reaction followed by a biphasic process occurs upon charge. Along with the structural refinement of the electrochemically reduced K₃Ti₂(PO₄)₃ phase, these new findings provide insight into the reaction mechanism in Na superionic conductor (NASICON)‐type KTi₂(PO₄)₃. The present approach can also be extended to the investigation of other NASICON‐type materials for potassium‐ion batteries.     

Influence of ZrO<Subscript>2</Subscript> addition on the structure,thermal stability,and dielectric properties of ZnTiO<Subscript>3</Subscript> ceramics

The zinc titanates doped with zirconium were synthesized by conventional solid-state reaction using metal oxides. X-ray diffractometry and differential scanning calorimetry analysis results indicated that the stable region of the hexagonal Zn(Zr _x Ti_1−x )O₃ phase extended to a high temperature (above 945 °C). The c/a value decreased as the Zr concentrations increased, which may be caused by the Zr⁴⁺ addition resulting in a shorter distance between the center ion and its nearest neighbors of the octahedron, and the bonding force between the B-site ion and oxygen ion of ABO₃ perovskite-like structure becoming stronger. The dielectric properties exhibited a significant dependence on the sintering temperatures and the amount of ZrO₂ addition. The dielectric constant decreased and Curie temperature (T _c) increased slightly with the increasing amounts of Zr ions. This is caused by the second phase of ZnZrO₃ which was deposited at the grain boundaries and inhibited the grain growth. Furthermore, diffuse phase transition with a maximum permittivity at a transition temperature that is close to room temperature in Zn(Zr _x Ti_1−x )O₃ was observed.     

Thermal expansion of ZrP2O7 and related solid solutions

The effect of solute ions on the thermal expansion of ZrP₂O₇ solid solutions was studied. The abrupt thermal expansion at the high-low inversion can be interpreted as due to the rotation of the polyhedra from the low-temperature form in the partially collapsed state to the high-temperature form in the fully expanded state. The replacement of zirconium ions by larger ions and/or the stuffing of cations into the cavities of the framework stabilized the expanded structure, and then depressed the abruptness of the expansion. Consequently the thermal expansion was reduced in Ce _x Zr_1-x P₂O₇ or (Li, Y) _x Zr_1-x P₂O₇ solid solutions.     

Metal Cation‐Assisted Synthesis of Amorphous B,N Co‐Doped Carbon Nanotubes for Superior Sodium Storage

Nearly inexhaustible sodium sources on earth make sodium ion batteries (SIBs) the best candidate for large‐scale energy storage. However, the main obstacles faced by SIBs are the low rate performance and poor cycle stability caused by the large size of Na⁺ ions. Herein, a universal strategy for synthesizing amorphous metals encapsulated into amorphous B, N co‐doped carbon (a‐M@a‐BCN; M = Co, Ni, Mn) nanotubes by metal cation‐assisted carbonization is explored. The methodology allows tailoring the structures (e.g., length, wall thickness, and metals doping) of a‐M@a‐BCN nannotubes at the molecular level. Furthermore, the amorphous metal sulfide encapsulated into a‐BCN (a‐MS_x@a‐BCN; MS_x: CoS, Ni₃S₂, MnS) nanotubes are obtained by one‐step sulfidation process. The a‐M@a‐BCN and a‐MS_x@a‐BCN possess the larger interlayer spacing (0.40 nm) amorphous carbon nanotube rich in heteroatoms active sites, making them exhibit excellent Na⁺ ions diffusion kinetics and capacitive storage behavior. As SIBs anodes, they show high capacity, excellent rate performance, and long cycle stability.     

Multichannel Porous TiO2 Hollow Nanofibers with Rich Oxygen Vacancies and High Grain Boundary Density Enabling Superior Sodium Storage Performance

TiO₂ as an anode for sodium‐ion batteries (NIBs) has attracted much recent attention, but poor cyclability and rate performance remain problematic owing to the intrinsic electronic conductivity and the sluggish diffusivity of Na ions in the TiO₂ matrix. Herein, a simple process is demonstrated to improve the sodium storage performance of TiO₂ by fabricating a 1D, multichannel, porous binary‐phase anatase‐TiO₂–rutile‐TiO₂ composite with oxygen‐deficient and high grain‐boundary density (denoted as a‐TiO_2?x /r‐TiO_2?x ) via electrospinning and subsequent vacuum treatment. The introduction of oxygen vacancies in the TiO₂ matrix enables enhanced intrinsic electronic conductivity and fast sodium‐ion diffusion kinetics. The porous structure offers easy access of the liquid electrolyte and a short transport path of Na⁺ through the pores toward the TiO₂ nanoparticle. Furthermore, the high density of grain boundaries between the anatase TiO₂ and rutile TiO₂ offer more interfaces for a novel interfacial storage. The a‐TiO_2?x /r‐TiO_2?x shows excellent long cycling stability (134 mAh g^?1 at 10 C after 4500 cycles) and superior rate performance (93 mAh g^?1 after 4500 cycles at 20 C) for sodium‐ion batteries. This simple and effective process could serve as a model for the modification of other materials applied in energy storage systems and other fields.     

Simultaneous uptake of ammonium and phosphate ions by composites of γ-alumina/potassium aluminosilicate gel

The simultaneous uptake of ammonium and phosphate ions from solution by composites of γ-alumina/potassium aluminosilicate (KAS) gel has been investigated. The composites were prepared by selective leaching of calcined kaolinite (Al₂Si₂O₅(OH)₄) using KOH solution, followed by neutralization of the leachate at pH 5.5 with nitric acid. The composites were reacted with solutions containing various concentrations of (NH₄)₂HPO₄ at pH 5, 7 and 10 at room temperature for 24 h to examine their uptake of ammonium and phosphate ions. Simultaneous uptake of ammonium and phosphate ions was found, the uptake of ammonium ions being greater than for phosphate ions, especially at pH=7. This observation is considered to result mainly from the porous properties of the composites, which should therefore be controlled to enhance the simultaneous uptake of both ions, especially phosphate ion.     

Iodine-Assisted Solid-State Synthesis and Characterization of Nanocrystalline Zirconium Diboride Nanosheets

A solid-state route was developed to prepare zirconium diboride nanosheets with the dimension of about 500 nm and thickness of about 20 nm from zirconium dioxide, iodine and sodium borohydride at 700°C in an autoclave reactor. The obtained ZrB₂ product was investigated by X-ray diffraction, scanning electron microscope and transmission electron microscopy. The obtained product was also studied by thermogravimetric analysis. It had good thermal stability and oxidation resistance below 400°C in air. Furthermore, the possible formation mechanism of ZrB₂ was also discussed.     

Synthesis of castable sodium zirconium phosphate monoliths employing reactions between zirconyl nitrate hydrate and condensed phosphates

Reactions between zirconyl nitrate hydrate and condensed phosphates can be used to produce castable low CTE sodium zirconium phosphate (NZP) monoliths. Reaction between sodium nitrate, zirconyl nitrate hydrate and condensed phosphoric acid at room temperature (alkali nitrate method) produces monoliths having a heterogeneous microstructure, which are multiphasic in appearance. Except for the presence of crystalline sodium nitrate, they are X-ray amorphous. Differential thermal analysis revealed two distinct exothermic crystallization events when these materials are heated. The first event, with an onset temperature of 650°C, is the result of NZP and ZrO₂crystallization. The second is the result of ZrP₂O₇ crystallization. Reaction between zirconyl nitrate hydrate and condensed sodium phosphate (condensed alkali phosphate method) results in a more homogeneous microstructure in which crystalline zirconium hydrogen phosphate hydrate and sodium nitrate are present. Two exothermic peaks, with onset temperatures of approximately 570 and 860°C, are observed. The first exotherm is the result of NZP, ZrO₂ and ZrP₂O₇ crystallization; the second exotherm is the result of a further NZP formation. After heating materials made by these two methods at 940°C for 24 h, the condensed-alkali-phosphate-method-derived material converted to phase-pure NZP, while the alkali-nitrate-method-derived material contained ZrP₂O₇. The differences in phase evolution between the materials prepared by these two methods are attributable to the differences in chemical and microstructural homogeneity that result from the reactants used. This revised version was published online in September 2006 with corrections to the Cover Date.     

Preparation of B2O3-P2O5-SiO2 coating films by the sol-gel method

ThexB₂O₃ · (20-x) P₂O₅ · 80SiO₂ (in mol%) glass films withx=0, 10 and 20 have been prepared from metal alkoxides by carrying out the coating in a dry atmosphere. These coating films have shown a larger value of load at scratch and a smaller shrinkage during heat-treatment by replacing P₂O₅ in the films with B₂O₃. It has been found that B₂O₃ more effectively reduces the glass transition temperature of SiO₂ glass than P₂O₅. The concentrations of sodium ions, which migrated from soda-lime-silica glass substrates during the film formation, were higher in phosphosilicate and borophosphosilicate films than in borosilicate and pure silica films. This finding should be ascribed to the gettering effects of phosphorus for sodium ions.