High-temperature tensile-hold crack-growth behavior of HASTELLOY<Superscript>®</Superscript> X alloy compared to HAYNES<Superscript>®</Superscript> 188 and HAYNES<Superscript>®</Superscript> 230<Superscript>®</Superscript> alloys

The creep–fatigue crack-growth tests of HASTELLOY^® X alloy were carried out at the temperatures of 649°C, 816°C, and 927°C in laboratory air. The experiments were conducted under a constant stress-intensity-factor-range (ΔK) control mode with a R-ratio of 0.05. In the constant ΔK tests, a ΔK of 27.5 MPa\(\sqrt{\mathrm{m}}\) and a triangular waveform with a frequency of 0.333 Hz were used. Various tensile hold times at the maximum load were imposed to study fatigue and creep–fatigue interactions. Crack lengths were measured by a direct current potential drop method. In this paper, effects of hold time and temperature on the crack-growth rates are discussed. Furthermore, the crack-growth rates of the HASTELLOY^® X alloy are compared to those of the HAYNES^® 188 and HAYNES^® 230^® superalloys.     

Stability of the LaCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> and LuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> Ions Studied by Mass Spectrometry

The enthalpy stability of the LaCl ₄ ^? and LuCl ₄ ^? ions is assessed using high-temperature mass spectrometry. The enthalpy of Cl^? detachment is determined to be Δ_rH⁰(298.15 K) = 332 ± 10 kJ/mol for LaCl ₄ ^? and 359 ± 10 kJ/mol for LuCl ₄ ^? .     

Use of a nanostructured material for separation of <Superscript>238</Superscript>U and <Superscript>237</Superscript>U produced by the photonuclear reaction <Superscript>238</Superscript>U(γ, <Emphasis Type="Italic">n</Emphasis>)<Superscript>237</Superscript>U

²³⁷U was produced by the reaction ²³⁸U(γ, n) on an electron accelerator, MT-25 microtron, at the Flerov Laboratory of Nuclear Reactions. For the separation of ²³⁷U and [²³⁸U, the recoil nuclei were collected by a nanostructured material, hydrated manganese dioxide (of the cryptomelane type), in the solid-solid system. From fission products, ²³⁷U was separated by ion exchange. The specific activity of the resulting ²³⁷U was 4.5 × 10⁹ Bq (mg ²³⁸U)^-1, with the content of radioactive impurities of ≤10^-6 Bq Bq^-1. The chemical yield of ²³⁷U was 80%.     

Formation-decomposition equilibrium of the NpO<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>·UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack> complex in chloride melts

The absorption spectra of the NpO ₂ ⁺ (5f ²) ion were examined in the region of the 3H ₅ ← ³ H ₄ magnetic dipole transition (1530–1760 nm) for series of melts with the UO ₂ ²⁺ concentration varied in the opposite directions: (1) NaCl-2CsCl eutectic melt with growing additions of the Cs₂UO₂Cl₄ complex salt and (2) Cs₂UO₂Cl₄ melt with growing additions of the NaCl-2CsCl mixture. Measurements of the integrated intensities of the bands belonging to the NpO ₂ ⁺ ·UO ₂ ²⁺ complex and unbound NpO ₂ ⁺ throughout the UO ₂ ²⁺ concentration range examined (up to 4.4 M in neat Cs₂UO₂Cl₄ melt) and processing of the data obtained in terms of the mass action law showed that the formation-decomposition reaction of the cation-cation complex can be described adequately only using the equation of reaction in the form NpO₂Cl ₄ ^3? + UO₂Cl ₄ ^2? ? {Cl₄ONpO?UO₂Cl₃}^4? = Cl^? (with the equilibrium constant of 1.3±0.1). Thus, the formation of the cationcation complex should be treated as replacement of chloride ion in the equatorial plane of uranyl(VI) by neptunyl(V), rather than as simple addition of UO ₂ ²⁺ to NpO ₂ ⁺ . The reverse reaction, decomposition of the cation-cation complex, consists essentially in replacement of neptunyl(V) by chloride ion.     

Estimating the effect of C<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and C<Stack><Subscript>3</Subscript><Superscript>+</Superscript></Stack> radicals and neutral clusters on the fullerene formation

The mass spectrum of the products of arc discharge in helium between graphite electrodes has been studied for various values of the gas flow rate. As the gas flow rate increases, the intensity of C₆₀^±, C₇₀^±, C₈₄^± and C₉₀^± fullerene peaks increases and that of the C₂⁻ and C₃⁺ cluster radicals decreases, but the total decay in radicals amounts to only 21% of the total growth of fullerenes. From this it follows that a contribution to the formation of fullerenes from the neutral clusters (which are taken into account for the first time) significantly exceeds the contribution due to small radical species.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>, Yb<Superscript>3+</Superscript>-doped and Nd<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript>-codoped high silica glass

The Nd³⁺, Yb³⁺-doped and Nd³⁺–Yb³⁺-codoped high silica glasses (HSGs) were fabricated by sintering porous glasses impregnated with Nd³⁺ and Yb³⁺ ions solutions. The Judd–Ofelt theory was used to study the spectroscopic properties of Nd³⁺-doped HSGs. Large parameter Ω₂ of Nd³⁺-doped HSGs suggests a lower centrosymmetric coordination environment around the Nd³⁺ in HSG. The spontaneous emission probability and emission cross-section (σ_em) of Yb³⁺-doped HSGs are obtained. A broad emission band from 950 to 1,100 nm was detected when the Nd³⁺–Yb³⁺-codoped HSG was excited by 808 nm LD. The energy transfer process from Nd³⁺ to Yb³⁺ in HSG was described in this paper.     

<Superscript>172</Superscript>Hf → <Superscript>172</Superscript>Lu Radionuclide Generator Based on a Reverse-Tandem Separation Scheme

The distribution coefficients of Hf(IV) and Lu(III) between Dowex 50W×8 cation exchanger or Dowex 1×8 anion exchanger and mixed HCl–H₂C₂O₄ solutions and between Dowex 50W×8 cation exchanger or Dowex 1×8 anion exchanger and citric acid solutions were determined. A number of modifications of the ¹⁷²Hf → ¹⁷²Lu generator, based on reverse separation schemes, were examined. Systems consisting of an anion-exchange resin and a solution of appropriate organic acid were taken as a chemical basis of the generator. Irreversible sorption of ¹⁷²Lu in generator columns was studied. The optimum operation mode of the ¹⁷²Hf → ¹⁷²Lu generator based on the reverse-tandem scheme with periodic transfer of the parent radionuclide into the liquid phase was determined.     

Comparison of an experimental bone cement with surgical Simplex<Superscript>®</Superscript> P,Spineplex<Superscript>®</Superscript> and Cortoss<Superscript>®</Superscript>

Conventional polymethylmethacrylate (PMMA) cements and more recently Bisphenol-a-glycidyl dimethacrylate (BIS-GMA) composite cements are employed in procedures such as vertebroplasty. Unfortunately, such materials have inherent drawbacks including, a high curing exotherm, the incorporation of toxic components in their formulations, and critically, exhibit a modulus mismatch between cement and bone. The literature suggests that aluminium free, zinc based glass polyalkenoate cements (Zn-GPC) may be suitable alternative materials for consideration in such applications as vertebroplasty. This paper, examines one formulation of Zn-GPC and compares its strengths, modulus, and biocompatibility with three commercially available bone cements, Spineplex, Simplex P and Cortoss. The setting times indicate that the current formulation of Zn-GPC sets in a time unsuitable for clinical deployment. However during setting, the peak exotherm was recorded to be 33 degrees C, the lowest of all cements examined, and well below the threshold level for tissue necrosis to occur. The data obtained from mechanical testing shows the Zn-GPC has strengths of 63 MPa in compression and 30 MPa in biaxial flexure. Importantly these strengths remain stable with maturation; similar long term stability was exhibited by both Spineplex and Simplex P. Conversely, the strengths of Cortoss were observed to rapidly diminish with time, a cause for clinical concern. In addition to strengths, the modulus of each material was determined. Only the Zn-GPC exhibited a modulus similar to vertebral trabecular bone, with all commercial materials exhibiting excessively high moduli. Such data indicates that the use of Zn-GPC may reduce adjacent fractures. The final investigation used the well established simulated body fluid (SBF) method to examine the ability of each material to bond with bone. The results indicate that the Zn-GPC is capable of producing a bone like apatite layer at its surface within 24 h which increased in coverage and density up to 7 days. Conversely, Spineplex, and Simplex P exhibit no apatite layer formation, while Cortoss exhibits only minimal formation of an apatite layer after 7 days incubation in SBF. This paper shows that Zn-GPC, with optimised setting times, are suitable candidate materials for further development as bone cements.     

Characterization of <Superscript>4</Superscript>I<Subscript>9/2</Subscript> ↔ <Superscript>4</Superscript>F<Subscript>3/2</Subscript> optical transitions in trivalent Nd<Superscript>3+</Superscript> ions in GaLaS glass

The positions of Stark levels have been determined, using a step-by-step procedure, in the ⁴I_9/2 and ⁴F_3/2 manifolds of Nd³⁺ ions from absorption and photoluminescence measurements in the 12–293 K temperature range. This data has been used to calculate the emission cross-section for which the maximum value turns out to be ～2.3 × 10^?20 cm². The radiative recombination time, calculated using Judd–Ofelt analysis, of the ⁴F_3/2 manifold is in close vicinity to the experimentally determined times that were measured by the conventional decay of PL after interruption of excitation and by QFRS. Moreover, the peak time defined by QFRS is independent of temperature. Therefore, the dominant relaxation mechanism from the ⁴F_3/2 excited manifold of Nd³⁺ ions in GaLaS glass is believed to be by radiative emission.     

Synthesis,electronic state,and particle size stabilization of nanoparticulate [Co(OH)<Subscript>2</Subscript>(H<Subscript>3</Subscript>O)<Stack><Subscript>δ</Subscript><Superscript>+</Superscript></Stack>]<Superscript>δ+</Superscript>

We have synthesized nanoparticulate cobalt(II) hydroxide containing Co²⁺ in tetrahedral oxygen coordination (Co _Td ²⁺ ), atypical of such systems: nano- [Co(OH)₂(H₃O) _δ ⁺ ]^δ+. The (Co _Td ²⁺ ) coordination in the hydroxide is inferred from its electronic diffuse reflectance spectrum, which shows a multiplet of strong absorption bands at 14500, 15000, and 16000 cm^?1 (⁴ A ₂(F)-⁴ T ₁(P) transition). Nanoparticulate cobalt(II) hydroxide forms in a weakly acidic medium under essentially nonequilibrium conditions due to supersaturation (by three to four orders of magnitude) with the starting reagents (CoCl₂ and LiOH) at the instant of the formation of the poorly soluble phase Co(OH)₂. Presumably, colloidal particles of nanoparticulate cobalt(II) hydroxide in a weakly acidic aqueous medium have a positive surface charge, compensated by a counter-ion (Cl^?) layer: nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ · δCl^?. The XRD patterns of pastes (gels) containing this hydroxide show three broad-ened lines with d = 5.31 (2θ = 16.7°), 2.77 (2θ = 32.3°), and 2.32 Å (2θ = 38.8°). According to small-angle X-ray scattering data, nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ has a narrow particle size distribution (1.0–2.0 nm). Synthesis and storage conditions are identified which ensure stabilization of the electronic state and particle size of nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ for a long time.     

Luminescent properties of single-phase Ba<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript>, R (R = Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) phosphors for white LED

The Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) phosphors were synthesized by use of a co-precipitation method. Crystal phase, excitation and emission spectra of sample phosphors are analyzed by means of XRD and FL, respectively. The emission spectra of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors exhibit four linear peaks attributed to the ⁵D₄?→?⁷F_J (J?=?6–3) transition of Tb³⁺ while four broad emission bands are observed in the emission spectra of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The effects of Eu²⁺ concentration on the luminescent properties of Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) are studied. Ce³⁺ affects the luminescent properties of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors just as the sensitizer. However, Eu²⁺ is considered both as the sensitizer and the activator in Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The chromaticity coordinates of Eu²⁺ and Tb³⁺ co-doped phosphors gather around the white light field with the CCT approximate to 5000 K, indicating that the luminescent property of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors may approach to a desired level needed for white LED application.     

Distribution of <Superscript>210</Superscript>Ро in lichen thalli

Distribution of ²¹⁰Po in thalli of soil and wood (epiphytic) lichens was studied. Four fractions containing the corresponding ²¹⁰Ро forms were obtained by sequential extraction: (1) intercellular, (2) extracellular, (3) intracellular, and (4) insoluble thallus residue. The ²¹⁰Ро uptake by lichens is mainly passive, as the total content of the radionuclide in fractions 1, 2, and 4 reaches 88–97%. From 3 to 12% of ²¹⁰Ро is taken up actively (fraction 3), and for soil lichens this parameter is approximately 2.75 times higher than for epiphytic lichens. Presumably, ²¹⁰Ро is supplied into soil and epiphytic lichens in the form of different chemical compounds and is therefore characterized by different bioavailability.     

Crystal structure of compounds CsA<Superscript>V</Superscript>A′<Superscript>VI</Superscript>O<Subscript>6</Subscript> (A<Superscript>V</Superscript> = Sb,Ta; A′<Superscript>VI</Superscript> = W,U)

Compounds CsA^VA′^VIO₆ (A^V = Sb, Ta; A′^VI = W, U) were synthesized by high-temperature solidphase reactions. The crystal structures of the compounds were refined by the Rietveld method (space group Fd \(\bar 3\) m).     

Controllable white light emission from Dy<Superscript>3+</Superscript>–Eu<Superscript>3+</Superscript> co-doped KCaBO<Subscript>3</Subscript> phosphor

Potassium calcium borate, KCaBO₃:Eu³⁺ phosphors with various Dy³⁺ concentrations (0–3 wt%) were synthesized by solid state reaction and studied for the first time. Under various UV–violet excitations, the obtained single monoclinic phased Dy³⁺–Eu³⁺ co-doped KCaBO₃ polycrystalline phosphors emit a combination of yellow–blue and red–orange wavelength giving intense white light, which can easily be controlled by varying the concentration of Dy³⁺. The increase in white light emission with the increase of Dy³⁺ concentration indicates the efficient energy inter-ion transfer from Dy³⁺ to Eu³⁺ ions. Furthermore, the observed emission lifetimes and the intense white light emission are suggestive exploration for the present phosphor for potential optoelectronic applications such as white light-emitting phosphor for blue LEDs chips.     

Effects of pH and concentration on ability of Cl<Superscript>−</Superscript> and NO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack> to intercalate into a hydrotalcite-like compound during its synthesis

In this study, we confirmed that the characteristics of anion intercalation into the interlayer of a hydrotalcite-like compound (HT) during synthesis are similar to those of the anion-exchange reaction of HTs as well as the reconstruction reaction of HTs from Mg-Al oxide. We demonstrated that (i) Cl⁻, which has a higher charge density than NO₃⁻, more easily reacted with Mg and Al species to form HT structure, resulting in greater intercalation of Cl⁻ into the HT interlayer; and (ii) for HTs with lower Mg: Al molar ratios, OH⁻, which has a higher charge density than Cl⁻ and NO₃⁻, was more likely to interact with Mg and Al species to form HT structure, blocking the intercalation of Cl⁻ and NO₃⁻. Furthermore, we showed that high concentrations of Cl⁻ and NO₃⁻ in solution regulated their intercalation into the HT interlayer. The high activity of Cl⁻ and NO₃⁻ in solution would facilitate the anions’ reactions with Mg and Al species to form HTs, resulting in a high degree of anion intercalation into the interlayer of HTs.     

The reaction Pu(VI) + Fe(CN)<Stack><Subscript>6</Subscript><Superscript>3−</Superscript></Stack> ⇄ Pu(VII) + Fe(CN)<Stack><Subscript>6</Subscript><Superscript>4−</Superscript></Stack> in NaOH solutions

A spectrophotometric study showed that, in 5 M NaOH, Pu(VII) prepared by ozonation of Pu(VI) is reduced with excess K₄Fe(CN)₆. The Pu(VII) content can be estimated from the amount of the Fe(CN)₆³⁻ formed. In NaOH solutions of concentration exceeding 8 M, the Fe(CN)₆³⁻ ion oxidizes Pu(VI). In 10.3 M NaOH, the tenfold excess of K₃Fe(CN)₆ fully converts 1 mM Pu(VI) to the heptavalent state within 4 min (rate constant 1.3 l mol⁻¹ s⁻¹ at 20°C). With an increase in the NaOH concentration, the oxidation rate increases, and smaller excess of K₃Fe(CN)₆ is required. This oxidant is consumed not only for Pu(VI) oxidation but also in reactions with H₂O and OH⁻ ions. Pu(VII) is unstable and is slowly reduced with water and with products of decomposition of iron complexes.     

Cathodoluminescence properties of SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript>and ZnO·SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript> phosphor nanopowders

The successful incorporation of ZnO nanoparticles in Pr³⁺-doped SiO₂ using a sol–gel process is reported. SiO₂:Pr³⁺ gels, with or without ZnO nanoparticles, were dried at room temperature and annealed at 600 °C. On the basis of the X-ray Diffraction (XRD) results, the SiO₂ was amorphous regardless of the incorporation of Pr³⁺ and nanocrystalline ZnO or annealing at 600 °C. The particles were mostly spherical and agglomerated as confirmed by Field Emission Scanning Electron Microscopy. Thermogravimetric analysis of dried gels performed in an N₂ atmosphere indicated that stable phases were formed at ≥900 °C. Absorption bands ascribed to ³H₄-³P_{(J = 0,1,2)}, ¹I₆ and ¹D₂ in the UV–VIS region were observed from SiO₂:Pr³⁺ colloids. The red cathodoluminescent (CL) emission corresponding to the ³P₀ → ³H₆ transition of Pr³⁺ was observed at 614 nm from dried and annealed SiO₂:Pr³⁺ powder samples. This emission was increased considerably when ZnO nanoparticles were incorporated. The CL intensity was measured at an accelerating voltage of 1-5 keV and a fixed beam current of 8.5 μA. The effects of accelerating voltage on the CL intensity and the CL degradation of SiO₂:Pr³⁺ and ZnO·SiO₂:Pr³⁺ were also investigated using Auger electron spectroscopy coupled with an Ocean Optics S2000 spectrometer.     

Y<Subscript>2</Subscript>O<Subscript>2</Subscript>S:Er<Superscript>3+</Superscript>,Ce<Superscript>3+</Superscript>—A new “invisible” IR phosphor

Ce³⁺ doping of Y₂O₂S:Er³⁺ can be used to suppress the visible anti-Stokes luminescence of the phosphor under excitation in the range 0.90–0.98 μm. We take advantage of this effect to create a new, efficient “invisible” IR phosphor emitting in the range 1.5–1.6 μm.     

Intense 2.0 µm emission from Ho<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Na<Subscript>5</Subscript>Lu<Subscript>9</Subscript>F<Subscript>32</Subscript> single crystal excited by 980 nm

This paper reported on optical spectra of Na₅Lu₉F₃₂ single crystals co-doped with ~?0.91 mol% Ho³⁺ and various Yb³⁺ concentrations by using an improved Bridgman method. The emission spectra and fluorescence decay curves were measured to investigate the luminescent properties of the Ho³⁺/Yb³⁺ co-doped Na₅Lu₉F₃₂ and the energy transfer process from Yb³⁺ to Ho³⁺ ion. Compared with the Ho³⁺ singly doped Na₅Lu₉F₃₂ crystal, the Ho³⁺/Yb³⁺ co-doped crystal had an obviously enhanced emission at 2.0 µm via the 980 nm laser diode excitation because of the efficient energy transfer from Yb³⁺ to Ho³⁺ ion. The maximum emission intensity at 2.0 µm was obtained at about 6.99 mol% Yb³⁺ concentration when the concentration of Ho³⁺ ions is fixed at ~?0.91 mol% in the current research. The maximum emission cross section of the above sample at 2.0 µm was calculated to be 1.23?×?10^?20 cm² according to the measured emission spectrum. The energy transfer efficiency from Yb³⁺:²F_5/2 to Ho³⁺:⁵I₆ for the crystal was estimated up to 90.8% indicating that Yb³⁺ ions can efficiently sensitize the Ho³⁺ ions.     

Probe Mössbauer Spectroscopy of BiNi<Subscript>0.96</Subscript><Superscript>57</Superscript>Fe<Subscript>0.04</Subscript>O<Subscript>3</Subscript>

This paper presents results of a ⁵⁷Fe probe Mössbauer spectroscopy study of the BiNi_0.96⁵⁷Fe_0.04O₃ nickelate. The spectra measured above its TN demonstrate that Fe³⁺ cations heterovalently substitute for Ni²⁺ nickel (←Fe³⁺), being stabilized on four sites of the nickel sublattice in the structure of BiNiO₃. Calculations in an ionic model with allowance for monopole and dipole contributions to the electric field gradient indicate that the parameters of electric hyperfine interactions between ⁵⁷Fe probe atom nuclei reflect the specifics of the local environment of the nickel in the structure of the unsubstituted BiNiO₃ nickelate. Below T^N, Mössbauer spectra transform into a complex Zeeman structure, which is analyzed in terms of first-order perturbation theory with allowance for electric quadrupole interactions as a small perturbation of the Zeeman levels of the ⁵⁷Fe hyperfine structure, as well as for specific features of the magnetic ordering of the Ni²⁺ cations in the nickelate studied.