Almost complete peritectic reaction in YBa2(Cu1−xFex)3O7−δ crystallization involving nanosized primary phase

Study on peritectic reaction is a matter of significant importance in materials science, which generally involves in the solidification of most functional oxide materials, for example, the YBa₂Cu₃O_7?δ (Y123) superconductor could be grown via a reaction of Y₂BaCuO₅ (Y211) + Liquid→Y123. Due to its crystallization characteristic, the growth of those materials does not entirely proceed, which severely impedes the development of industrialized process. Thus the realization of a complete peritectic reaction is an interesting issue for both theory and experiment. Here, we report an almost complete peritectic reaction occurring in the growth of YBa₂(Cu_1?xFe_x)₃O_7?δ crystals using modified melt‐growth. Our findings remarkably show that Y211 almost fully reacted with liquid to generate Y123, remaining approximately 1 vol%, evidently lower than that in the normal case. The nature of this unconventional phenomenon is clarified that the Fe‐doping elevates the nucleation barrier in the peritectic melting of Y123 and causes a massive homogeneous nucleation catastrophe, leading to nanosized and dispersive Y211 particles, which readily and almost fully dissolve in the subsequent peritectic solidification of Y123. Most importantly, the new conception derived from this work is promising for reviving other functional materials, which are disregarded due to their incomplete peritectic reactions.     

Calcium dicarboxylates nucleation of β‐polypropylene

Seven dicarboxylates of calcium were synthesized. The effect of dicarboxylate on the formation of β‐form polypropylene was investigated by X‐ray diffraction. Calcium pimelate, calcium suberate, calcium phthalate, and calcium terephthalate have been found to be an effective β‐nucleator. The K_x values of the isotatic propylene samples with 0.5 wt % of the nucleators above are 0.95, 0.96, 0.93, and 0.62, respectively. Calcium succinate, calcium adipate, and calcium sebacate behave invalidly on the nucleating of the β‐phase. We conducted an investigation on the affect of particle shape, crystal form, and crystallinity upon the level of the β‐form. The X‐ray diffraction of the effective nucleators reveals a common character that their first reflection locate at the d‐spacing between 10 to 13 Å, indicating structural similarity of the nucleators with β‐polypropylene. The nucleation mechanism is explained by the cooperative effect of the nonpolar and polar part of nucleating agents in the crystallization of polypropylene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 633–638, 2002     

Preparation and characterisation of the perovskite oxide superconductor YBa2Cu3O7 − x

A perovskite oxide, YBa₂Cu₃O_{7 ? x} (YBCO), has been prepared by the method of carbonate precipitation from a mixed nitrate solution and oxidised at 950°C in an air atmosphere to obtain a perovskite oxide to be used as a catalyst for H₂/CO reactions. The characterisation of the perovskite oxide was performed by using X-ray diffraction before and after the treatment with different gases, A.C. susceptibility measurements, particle size measurements and temperature programmed reduction (TPR) in which hydrogen was used in order to monitor the changes of the perovskite with temperature in a hydrogen atmosphere. A.C. susceptibility measurements showed that the YBCO perovskite exhibited the typical good superconducting sharp transition temperature at 93 K, indicating that the wet chemical preparation route is suited to the production of this material.     

Characterization of ZrN,ZrO2 and β′–Zr7O11N2 nanoparticles synthesized by pulsed wire discharge

Nanoparticles of ZrN, ZrO₂ and β′–Zr₇O₁₁N₂ were synthesized by pulsed wire discharge using Zr wire in various O₂ and N₂ gas mixtures with different oxygen partial pressures of up to 40 kPa and a total pressure of 100 kPa. The syntheses were carried out at a relative energy ratio (K) of 6.4 which was defined by a charged energy in a capacitor of the synthesis apparatus divided by the evaporation energy of the Zr wire. Morphology and phase analyses were carried out on these nanoparticles by X‐ray diffraction and field‐emission transmission electron microscopy. ZrN and Zr₂N were observed in a sample synthesized in 100% N₂ gas while with increasing the O₂ from 1% of total pressure, formation of β′–Zr₇O₁₁N₂ and ZrO₂ was seen. By bright field image observation, electron energy loss spectroscopy (EELS) and selected area electron‐diffraction analyses, nanoparticles of ZrN, β′–Zr₇O₁₁N₂ and ZrO₂ were separately characterized. In these syntheses, nanoparticles of β′–Zr₇O₁₁N₂ existed in much smaller size and different shape than the ordinary spherical nanoparticles of ZrN and ZrO₂. In gas mixtures where O₂ contents were larger than 22% (dry air composition), ZrN was not detected or detected with just a fractional amount compared to the two major phases of β′‐Zr₇O₁₁N₂ and ZrO₂. EELS data for ZrN and β′–Zr₇O₁₁N₂ were obtained and compared by separated analyses of nanoparticles of these phases. From these data, it was concluded that, in nuclear accidents, small amount of particles can indicate the accident atmosphere around the Zr alloys fuel cladding.     

Plastic Forming of High‐Tc YBa2Cu3O7−x Bulk Superconductors

The large bulk high‐T_c YBa₂Cu₃O_7?x (YBCO) superconductor samples were prepared by plastic‐forming method. We examined the effects of the solvent and the crystallinity of YBCO powder on the composition, crystallinity, and superconducting properties of YBCO sheet samples (sample size: 50 mm × 50 mm× 3 mm). By changing the solvent from water to turpentine oil, the leaching of Ba²⁺ ions from YBa₂Cu₃(OH)_y multimetallic hydroxide particles used as an inorganic binder and the YBCO powder were reduced. This results in the composition of the grain boundaries of fired YBCO sheet samples to be the same as the composition of YBa₂Cu₃(OH)_y multimetallic hydroxide particles. Changing nondoped YBCO powder prepared by sintering to 5 wt% Pt‐doped YBCO powder prepared by melt texturing, J_c value of YBCO sheet samples changed from about 700 to 6,106 A/cm² at 77 K.     

Structural and Spectroscopic Properties of δ‐Y2Si2O7 Nanopowders Activated with Nd3+ Ions

Phosphors of δ‐Y₂Si₂O₇ doped with Nd³⁺ ions were prepared in the SiO₂–Y₂O₃ binary systems using the solgel technique. Nano‐sized crystalline phosphor powders were obtained by annealing the dried gels at 1480°C. The average grain sizes of the NYS1, NYS2, NYS3, and NYS4, powders were estimated to be 44.1, 41.3, 48.1, and 53.2 nm from the grain size distribution curves, respectively, and these results were confirmed by transmission electron microscope measurements. The spectroscopic properties of the powders were studied by measuring the luminescence spectra, and the decay curves of the ⁴F_3/2 emission level were measured at room temperature.     

Preparation of polyethylene oxide/LixV2‐δO4‐δ nanocomposites

Polyethylene oxide (PEO)/LixV_2‐δO_4‐δ nanocomposites were prepared in aqueous solution. Characterization of the nanocomposites using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), powder X‐ray diffraction (XRD), and Fourier transform infrared spectrum (FTIR) shows that polymer chains intercalate inorganic host lamella and exhibit lattice expansion along the stacking direction of 4.2 Å. A possible model for the structure of the nanocomposite is also provided. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2162–2166, 2001     

Effect of nucleating duality on the formation of γ‐phase in a β‐nucleated isotactic polypropylene copolymer

BACKGROUND: It is a challenge for polymer processing to promote the formation of γ‐phase under atmospheric conditions in isotactic polypropylene (iPP) copolymer containing chain errors. Incorporation of an α‐nucleator in iPP copolymer seems reasonable since it can enhance non‐isothermal crystallization. Up to now, however, the issue regarding a β‐nucleated iPP copolymer still remains unclear, which is the subject of this study. RESULTS: The results indicate that the γ‐phase indeed occurs in a β‐nucleated random iPP copolymer with ethylene co‐unit (PPR) sample and becomes predominant at slow cooling rates (e.g. 1 °C min^?1) where the formation of the β‐form is suppressed to a large extent. With detailed morphological observations the formation of γ‐phase in the β‐nucleated PPR sample at slow cooling rate is unambiguously attributed to the nucleating duality of the β‐nucleator towards α‐ and β‐polymorphs. The α‐crystals, induced by the β‐nucleator, serve as seeds for the predominant growth of the γ‐phase. Moreover, the presence of the β‐nucleator, acting as heterogeneous nuclei, promotes the formation of γ‐phase in the nucleated PPR sample, at least to some extent. CONCLUSION: The findings in this study extend our insights into the formation of γ‐phase in β‐nucleated iPP copolymer and, most importantly, provide an alternative route to obtain iPP rich in γ‐phase. Copyright © 2008 Society of Chemical Industry     

The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene

The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002     

Selective Corrosion Preparation and Sintering of Disperse α‐Al2O3 Nanoparticles

Disperse fine equiaxed α‐Al₂O₃ nanoparticles with a mean particle size of 9 nm and a narrow size distribution of 2–27 nm were synthesized using α‐Fe₂O₃ as seeds and isolation via homogeneous precipitation‐calcination‐selective corrosion processing. The presence of α‐Fe₂O₃ acting as seeds and isolation phase can reduce the formation temperature to 700°C and prevent agglomeration and growth of α‐Al₂O₃ nanoparticles, resulting in disperse fine equiaxed α‐Al₂O₃ nanoparticles. These α‐Al₂O₃ nanoparticles were pressed into green compacts at 500 MPa and sintered first by normal sintering to study their sintering behavior and finally by two‐step sintering (heated to 1175°C without hold and decreased to 1025°C with a 20 h hold in air) to obtain nanocrystalline α‐Al₂O₃ ceramics. The two‐step sintered bodies are nanocrystalline α‐Al₂O₃ with an average grain size of 55 nm and a relative density of 99.6%. The almost fully dense nanocrystalline α‐Al₂O₃ ceramic with finest grains achieved so far by pressureless sintering reveals that these α‐Al₂O₃ nanoparticles have an excellent sintering activity.     

Nano‐engineered nickel catalysts supported on 4‐channel α‐Al2O3 hollow fibers for dry reforming of methane

A nickel (Ni) nanoparticle catalyst, supported on 4‐channel α‐Al₂O₃ hollow fibers, was synthesized by atomic layer deposition (ALD). Highly dispersed Ni nanoparticles were successfully deposited on the outside surfaces and the inside porous structures of hollow fibers. The catalyst was employed to catalyze the dry reforming of methane (DRM) reaction and showed a methane reforming rate of 2040 Lh^?1gNi^?1 at 800°C. NiAl₂O₄ spinel was formed when Ni nanoparticles were deposited on alpha‐alumina substrates by ALD, which enhanced the Ni‐support interaction. Different cycles (two, five, and ten) of Al₂O₃ ALD films were applied on the Ni/hollow fiber catalysts to further improve the interaction between the Ni nanoparticles and the hollow fiber support. Both the catalyst activity and stability were improved with the deposition of Al₂O₃ ALD films. Among the Al₂O₃ ALD coated catalysts, the catalyst with five cycles of Al₂O₃ ALD showed the best performance. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2625–2631, 2018     

Equiaxed β–Si3N4 ceramics prepared by rapid reaction‐bonding and post‐sintering using TiO2–Y2O3–Al2O3 additives

Sintered reaction‐bonded Si₃N₄ ceramics with equiaxed microstructure were prepared with TiO₂–Y₂O₃–Al₂O₃ additions by rapid nitridation at 1400°C for 2 hours and subsequent post‐sintering at 1850°C for 2 hours under N₂ pressure of 3 MPa. It was found that α–Si₃N₄, β–Si₃N₄, Si₂N₂O, and TiN phases were formed by rapid nitridation of Si powders with single TiO₂ additives. However, the combination of TiO₂ and Y₂O₃–Al₂O₃ additives led to the formation of 100% β–Si₃N₄ phase from the nitridation of Si powders at such low temperature (1400°C), and the removal of Si₂N₂O phase. As a result, dense β–Si₃N₄ ceramics with equiaxed microstructure were obtained after post‐sintering at high temperature.     

Bi2Ti2O7‐based pyrochlore nanoparticles and their superior photocatalytic activity under visible light

Nanoparticles of Bi₂Ti₂O₇ pyrochlore were synthesized by a coprecipitation method. They exhibit a high visible‐light photoactivity for decolorization of a methyl‐orange dye solution in the presence of a sacrificial agent, H₂O₂. The same pyrochlore system with an Ag co‐catalyst showed even faster kinetics under only visible light and an unprecedentedly high photoactivity in the UV range.     

Characteristics of Y1Ba2Cu3O7-x high-T c superconductor prepared by partial melting process

The superconducting Y₁Ba₂Cu₃O_7-x (123) and the Y₂Ba₁Cu₁O₅(211) powders in this study were prepared by pyrophoric synthesis method with Y₂O₃ (99.9 %), BaCO₃ (99.9 %), and CuO (99.9 %) powders. Samples of 123 and 211 pellets were first prepared and then piled to have a 123/211/123 arrangement before a partial melting process was applied for phase change of the center piece (211) to 123 phase through a peritectic reaction. The process parameters were a melting temperature of 1,040–1,070 °C and the mass of the 123 piece ranging from 0.4 to 1.2 g. The superconductivity, such as critical temperature (T_c), and mass susceptibility(χ) of bulk 123 and 211 samples were measured by AC four point probe method and AC susceptometer, respectively. The experimental results can be summarized as follows: the best preparation condition in the range examined was a melting temperature of 1,060 °C and mass ratio [123(A)/211(B)] of 2:1 with melting time of 30 minutes to yield the T_c of 88.5 K.     

Influence of sintering additives on densification kinetics and high‐temperature strength in γ‐Y2Si2O7 ceramics

Pressureless sintering of pure γ‐Y₂Si₂O₇ powders that had been synthesized by a solid‐liquid reaction method using Y₂O₃ and SiO₂ powders with Li₂O, MgO, and Al₂O₃ additives was reported. The sintering kinetics of γ‐Y₂Si₂O₇ powders was analyzed to track details of densification evolution. Apparent activation energies of the densification of γ‐Y₂Si₂O₇ powders were reported for the first time, which was 57.1, 96.6, and 100.2 kJ/mol for the powders with Li₂O, MgO, and Al₂O₃ additives, respectively, indicating that Li₂O could promote the densification behavior effectively. The flexural strengths as a function of temperature for the γ‐Y₂Si₂O₇ ceramics with different additives were also investigated. The degradation of high‐temperature flexural strength was mainly ascribed to the softening of grain‐boundary glassy phase. γ‐Y₂Si₂O₇ specimens fabricated using the powders with MgO or Al₂O₃ additives exhibited better high‐temperature mechanical properties.     

Synthesis,characterization, and corrosion inhibition study of polyaniline‐α‐Fe2O3 nanocomposite

Polyaniline (PANI)‐α‐Fe₂O₃ nanocomposites (NCs) have been synthesized by chemical oxidative in situ polymerization of aniline in presence of α‐Fe₂O₃ nanoparticles at 5°C using (NH₄)₂S₂O₈ as an oxidant in an aqueous solution of sodium dodecylbenzene sulphonic acid (SDBS), as surfactant and dopant under N₂ atmosphere. The room temperature conductivity of NCs decreases and coercive force (H_c) increases with an increase addition of α‐Fe₂O₃ in PANI matrix. The result of FTIR and TGA shows that the interaction between α‐Fe₂O₃ particles and PANI matrix could improve the thermal stability of NCs. NCs demonstrate the superparamagnetic behavior. The performance of PANI and PANI‐α‐Fe₂O₃ NCs as protective coating, against corrosion of 316LN stainless steel in 3.5% NaCl was assessed by potentiodynamic polarization technique. The study shows a good corrosion inhibition effect of both the coatings. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Processing YAG/α‐Al2O3 composites via reactive sintering Y2O3/Al2O3 NP mixtures. A superior alternative to bottom up processing using atomically mixed YAlOx NPs

This effort contrasts “bottom‐up” processing of YAG/α‐Al₂O₃ composites where both elements (as 40‐50 nm APSs nanopowders) are present at close to atomic mixing with reactive sintering where ball‐milled mixtures of the individual nanopowders (40‐50 nm APSs) give uniform elemental mixing at length scales closer to 100‐800 nm with correspondingly much longer diffusion distances. In contrast to expectations, densification with control of final grain sizes is best effected using reactive sintering. Thus, reactive sintering to densities ≥95% occurs at only 1500°C with final grain sizes of ≈1000 nm for all samples. In contrast “bottom up” processing to ≥95% densities is only achieved at 1600°C, and with final grain sizes of 1700 nm. The reason for this unexpected behavior is that YAG phase forms early in the bottom up approach greatly inhibiting diffusion promoted densification. In contrast, in reactive sintering, YAG is prevented from forming because of the longer diffusion distances such that densification occurs prior to full conversion of the Y₂O₃ component to YAG. The found hardness values are statistically superior to literature values for composites near the known eutectic composition. In an accompanying paper, the addition of a third component reverses this behavior.     

Diastereoselective and Enantioselective Epoxidation of Acyclic β‐Trifluoromethyl‐β,β‐Disubstituted Enones by Hydrogen Peroxide with a Pentafluorinated Quinidine‐Derived Phase‐Transfer Catalyst

An efficient catalytic asymmetric epoxidation of β‐trifluoromethyl‐β,β‐disubstituted unsaturated ketones has been achieved by a pentafluorine‐substituted phase‐transfer catalyst with hydrogen peroxide (30%). Thus, the β‐trifluoromethyl‐α,β‐epoxy ketones with a quaternary carbon centre were obtained in excellent diastereoselectivities (up to 100:1 dr) and excellent enantioselectivities (up to 99.7% ee). Low catalyst loading, recycle of catalyst, environmentally benign oxidant and easy transformation of the epoxides into medicinally important trifluoromethylated intermediate make our protocol much more practical.     

Effect of Ba Nonstoichiometry in Bax(Zr0.8Y0.2)O3−δ on Population of 5‐Coordinated Y

The local environments of Y in the Y‐substituted BaZrO₃ of the starting compositions of Ba_x(Zr_0.8Y_0.2)O_3?δ (x = 0.97, 1.0, 1.03, and 1.06) were analyzed by ⁸⁹Y magic angle spinning NMR spectroscopy. The result showed a strong population dependence of 5‐coordinated Y³⁺ ions mostly at the B site on the Ba contents. The enhancement of Ba contents by 9 at% (from 0.97 to 1.06 in the starting Ba contents) in a nominal composition increased the amount of 5‐coordinated Y³⁺ ions from 35% ± 7% to 49% ± 5%, suggesting the importance of maximizing the Ba contents to populate more oxygen vacancies which is related to the concentration of protons incorporated during the hydration process. The wide variation in the lattice parameter of yttrium‐substituted BaZrO₃ perovskite materials in previous reports was reinterpreted with the variation in the Ba contents resulting from the evaporation of BaO during the sintering processes. Y³⁺ ions were confirmed to replace mainly the Zr⁴⁺ ions, as expected, and a tendency of oxygen vacancy clustering near the Y³⁺ ions was discussed.     

Recrystallization behavior of β‐isotactic polypropylene in homogeneous and heterogeneous matrix–fiber composites

β‐isotactic polypropylene (β‐iPP) cylindritic crystals were produced in homogeneous iPP fiber–matrix composites and heterogeneous polyamide (PA)–iPP fiber–matrix composites under different sample preparation conditions. The melt recrystallization behaviors of the β‐iPP crystals obtained in the homogeneous and heterogeneous composites were studied by optical microscopy. The experimental results show that, by heating the sample to 180 °C, the birefringence contributed by the iPP crystals in both α‐ and β‐forms disappears completely. During the cooling process, the β‐iPP crystals in the homogeneous composite appear again, while the iPP in the heterogeneous composite crystallizes in its α‐form. This demonstrates the different origins of the β‐iPP cylindrites in the homogeneous and heterogeneous composites. While the β‐iPP cylindrites in the heterogeneous composite are associated with the sample preparation procedure, the β‐iPP cylindrites in the homogeneous composite are produced by recrystallization of the molten but incompletely relaxed iPP fibers. In situ observation of the melt recrystallization process shows that the molten iPP oriented fibers crystallize first during the cooling process at relatively higher temperature in the α‐form. Abundant randomly dispersed β‐iPP nuclei formed at the surface of the recrystallized iPP fibers, which generate the β‐iPP cylindrites. Copyright © 2012 Society of Chemical Industry