Synthesis of New Pb-based 1222 Layered Cuprates in the (Pb,S)Sr2(RE,Ce)2Cu2O z (RE=Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Y) System

A new family of the Pb-based layered cuprate with the 1222 structure has been synthesized in the (Pb,S)Sr₂(RE,Ce)₂Cu₂O _z (RE=Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Y) system. The almost-single phase samples are obtained for x=0.25 and y=1.0 in the composition of (Pb_1?x S _x )Sr₂(RE_2?y Ce _y )Cu₂O _z . Each of the samples has the crystal structure with a tetragonal symmetry. Both of the lattice parameters a and c are decreasing with the decrease of the ionic radius of RE element. Among these samples, the sample with RE=Er has the smallest resistivity in the whole temperature range and the slope of the resistivity versus temperature is the most gentle. Despite annealing under O₂ atmosphere at high-pressure of 121 atm, this sample is a semiconductor with the transport process characteristics of three-dimensional variable range hopping conduction. Then the samples of RE=Er with smaller y are investigated for the composition of (Pb_0.75S_0.25)Sr₂(RE_2?y Ce _y )Cu₂O _z , the sample with y=0.4 is found to show an onset of resistivity drop phenomenon at about 11 K with the decrease of temperature. Moreover, we also discover that the samples of RE=Ho with y=0.4 show an onset of the resistivity dropping at over 20 K and zero resistivity at 13 K. From these results, the present (Pb_0.75S_0.25)Sr₂(RE_2?y Ce _y )Cu₂O _z system is considered to be a new family of the Pb-based superconducting cuprates with the 1222 structure.     

Magnetic susceptibility of heavy rare-earth molybdates

Results of the molar magnetic susceptibility (_m) measurements of heavy rare-earth (RE) molybdates of the type RE₂ (MoO₄)₃ with RE = Gd, Dy, Ho, Er, Tm and Yb are reported in the temperature range 3 to 300 K at a magnetic field of 3.2X10⁵ Am^–1. All molybdates show ferrimagnetic behaviour with ferrimagnetic Néel temperatures lying in the range 15 to 24 K. Evaluated magneton numbers agree fairly well with those for free tripositive rare-earth ions. Various magnetic parameters are evaluated using appropriate models.     

The Effect of Linker-to-Metal Energy Transfer on the Photooxidation Performance of an Isostructural Series of Pyrene-Based Rare-Earth Metal–Organic Frameworks

The tetratopic linker, 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H₄TBAPy) along with rare-earth (RE) ions is used for the synthesis of 9 isostructures of a metal–organic framework (MOF) with shp topology, named RE-CU-10 (RE = Y(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III)). The synthesis of each RE-CU-10 analogue requires different reaction conditions to achieve phase pure products. Single crystal X-ray diffraction indicates the presence of a RE₉-cluster in Y- to Tm-CU-10, while a RE₁₁-cluster is observed for Yb- and Lu-CU-10. The photooxidation performance of RE-CU-10 analogues is evaluated, observing competition between linker-to-metal energy transfer versus the generation of singlet oxygen. The singlet oxygen produced is used to detoxify a mustard gas simulant 2-chloroethylethyl sulfide, with half-lives ranging from 4.0 to 5.8 min, some of the fastest reported to date using UV-irradiation and < 1 mol% catalyst, in methanol under O₂ saturation.     

Synthesis of New Pb-Based 1222 Cuprates Containing Phosphorus, (Pb0.75P0.25)Sr2(RE2–x–y Ce x Sr y )Cu2O z (RE = Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y)

New Pb-based 1222 cuprates containing phosphorus have been synthesized in the (Pb_0.75P_0.25)Sr₂- (RE_2–x–y Ce _x Sr _y )Cu₂O _z (RE = Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y) systems. The almost-single phase samples are obtained for 0.5≤x≤1.0 and y=0.1 in the cases of RE = Nd, Dy, Ho, Er, Tm, Yb and Y, while for 0.3≤x≤1.0 and y=0.1 in the cases of RE = Sm, Eu and Gd. The samples crystallize in a tetragonal lattice, the lattice parameters a and c are decreasing with the decrease of the ionic radius of the RE element. Even after annealing under 143 atm O₂ atmosphere at 400 °C, almost all the samples with the common values x=0.5 and y=0.1 are semiconductors with a transport process followed by three-dimensional variable range hopping. However, the samples of RE = Sm, Eu and Gd, which are of almost single 1222 phase, even for x=0.3 and y=0.1, show superconductivity with the onsets at about 25 K, 20 K and 22 K, respectively. Through this study, we find very important procedure for discovery of new superconducting 1222 compound.     

Thermal and Mechanical Properties Optimization of ABO4 Type EuNbO4 By the B-Site Substitution of Ta

Ferroelastic ABO₄ type RETaO₄ and RENbO₄ ceramics (where RE stands for rare earth) are being investigated as promising thermal barrier coatings (TBCs), and the mechanical properties of RETaO₄ have been found to be better than those of RENbO₄. In this work, B-site substitution of tantalum (Ta) is used to optimize the thermal and mechanical properties of EuNbO₄ fabricated through a solid-state reaction (SSR). The crystal structure is clarified by means of X-ray diffraction (XRD) and Raman spectroscopy; and the surface microstructure is surveyed via scanning electronic microscope (SEM). The Young’s modulus and the thermal expansion coefficient (TEC) of EuNbO₄ are effectively increased; with respective maximum values of 169 GPa and 11.2 × 10⁻⁶ K⁻¹ (at 1200 °C). The thermal conductivity is reduced to 1.52 W·K⁻¹·m⁻¹ (at 700 °C), and the thermal radiation resistance is improved. The relationship between the phonon thermal diffusivity and temperature was established in order to determine the intrinsic phonon thermal conductivity by eliminating the thermal radiation effects. The results indicate that the thermal and mechanical properties of EuNbO₄ can be effectually optimized via the B-site substitution of Ta, and that this proposed material can be applied as a high-temperature structural ceramic in future.     

Magnetic properties of RE2Mo2O7 pyrochlores

The magnetic properties of RE₂Mo₂O₇ (RE=Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, and Yb³⁺) and of solid solutions of the type (Nd_1?x A _x )₂Mo₂O₇ (A=Yb or Er; 0.05≤x≤0.4) have been studied using an ac mutual inductance bridge. All the compounds were found to exhibit magnetic ordering in the neighborhood of or below 77 K. The data have been analyzed using (i) the available susceptibility data on Y₂Mo₂O₇, (ii) a ferromagnetic coupling among the Mo⁴⁺ ions to obtain the contribution from the RE³⁺ ion, and (iii) the available susceptibility data on RE₂Ti₂O₇ to obtain the contribution from the Mo⁴⁺ ions. It was found that procedure (iii) gave the most satisfactory explanation of the magnetic ordering. The results indicated that (1) the Mo⁴⁺ ions become ordered magnetically, (2) the behavior of the RE³⁺ ions is almost the same as in the isostructural RE₂Ti₂O₇ and RE₂V₂O₇ compounds, and (3) the susceptibility values differ appreciably as we go from Nd³⁺ to Yb³⁺, possibly due to narrowing of the π* Mo-O conduction band.     

Development of high mechanical properties and moderate thermal conductivity cast Mg alloy with multiple RE via heat treatment

A new cast Mg–2 Gd–2 Nd–2 Y–1 Ho–1 Er–0.5 Zn–0.4 Zr(wt%) alloy was prepared by direct-chill semicontinuous casting technology. The microstructure, mechanical properties and thermal conductivity of the alloy in as-cast, solid-solution treated and especially peak-aged conditions were investigated. The as-cast alloy mainly consists of β-Mg matrix,(Mg, Zn)_3 RE phase and basal plane stacking faults. After proper solid-solution treatment, the microstructure becomes almost Mg-based single phase solid solution except just very few RE-riched particles. The as-cast and solid-solution treated alloys exhibit moderate tensile properties and thermal conductivity. It is noteworthy that the Mg alloy with 8 wt% multiple RE exhibits remarkable age-hardening response( HV = 35.7), which demonstrates that the multiple RE(RE = Gd, Nd, Y, Ho, Er) alloying instead of single Gd can effectively improve the age-hardening response.The peak-aged alloy has a relatively good combination of high strength/hardness(UTS(ultimate tensile strength) 300 MPa; TYS(tensile yield strength) 210 MPa; 115.3 HV), proper ductility(ε≈ 6%) and moderate thermal conductivity(52.5 W/(m K)). The relative mechanisms mainly involving aging precipitation of β￠ and β' phases were discussed. The results provide a basis for development of high performance cast Mg alloys.     

Structure,superconductivity and magnetism of new rare earth-rhodium silicides RE2Rh3Si5 of U2Co3Si5-type

New ternary silicides RE₂Rh₃Si₅ (RE = Y, La, Nd, Sm, Gd, Tb, Dy, Ho, Er) have been prepared. They crystalize in the U₂Co₃Si₅-type structure. Only the silicides containing the diamagnetic rare earths Y and La show a superconducting transition at T_Cr = 4.4 ± 0.2K and T_Cr = 2.7 ± 0.1K respectively, those with magnetic rare earths order antiferromagnetically at low temperature.     

Electrical transport studies on heavy rare-earth tungstates

This paper reports the measurement of thermoelectric-power (S) at different temperatures (800–1100 K) and electrical conductivity (σ) as a function of electric field strength, time, ac signal frequency and temperature (650–1200 K) for pressed pellets of heavy rare-earth tungstates (HRET) with a general formula RE₂(WO₄)₃ [where RE = Tb, Dy, Ho, Er, Tm and Yb]. These tungstates are typical insulating compounds with room-temperature σ value less than 10^?10 ohm^?1 cm^?1 and become semiconductors at elevated temperature with σ values of the order of 10^?5 ohm^?1 cm^?1 at 1200 K. The S vs T^?1 and log σ vs T^?1 plots are linear, but a change in the slope of straight lines occurs at a temperature (T_B) which lies between 900–1025 K for different tungstates. These break temperatures are the same for both S and σ plots. It has been found that HRET are mixed ionic-electronic conductors. Above T_B the electronic conduction dominates over the ionic conduction, but below T_B both become comparable. The electronic conduction above T_B is intrinsic with large polaron holes as the principal charge carriers; they conduct via a band mechanism. The energy band gap lies in the range 3.2 to 4.0 eV, and the charge carrier mobility in the range 3.8×10^?2 to 2.5 cm²/V-Sec for the different tungstates. Below T_B both electronic and ionic conduction are extrinsic. The electrons conduct via a thermally activated hopping mechanism with an activation energy lying in the range 0.87 to 1.30 eV, and the holes via a diffusion process with an activation energy lying in the range 0.88 to 1.23 eV for the different tungstates.     

Superplasticity of a Zn-1.1 WT.% Al alloy at high temperatures

The Zn-1.1 wt.% Al alloy exhibits superplastic properties in the temperature range from 292 K (0.42 Tm) to 635 K (0.92 Tm). The best properties were observed at the temperature of 520 K (0.75 Tm). The parameter m reaches the value m = 0.73 at the true strain-rate ϵ = 7 × 10⁻⁵s⁻¹, and the maximum ductility is A = 1020% at the initial strain-rate ϵ₀ = 1.7 × 10⁻⁴s⁻¹. This value is the highest one observed in low-alloyed ZnAl alloys and shows that materials with great volume fraction of the second phase with very good superplastic properties can be reached at comparably high homologous temperatures also in low-alloyed materials. The extreme values of m and A were observed in the material with the initial mean grain size d = 17 um.     

Synthesis and oxygenation behavior of RBaCo4O7 + δ (R = Y, Dy-Lu)

We have studied phase formation processes in the R₂O₃-BaO-CoO = 0.5: 1: 4 (R = Y, Gd-Lu) systems at temperatures from 900 to 1100°C, optimized solid-state synthesis conditions for RBaCo₄O_{7 + δ} (R114), and obtained single-phase samples for R = Y, Dy, Ho, Er, Tm, Yb, and Lu. The behavior of R114 (R = Y, Dy, Lu) materials during thermal cycling and oxygenation has been investigated.     

Negative thermal expansion in Y2W3O12

Neutron diffraction data were collected on polycrystalline Y₂W₃O₁₂ at seven temperatures from 15 to 1373 K. All three cell edges of orthorhombic Y₂W₃O₁₂ decrease with increasing temperature, giving an average linear thermal expansion coefficient of −7.0×10⁻⁶ K⁻¹. Rietveld refinements of the neutron diffraction data show an apparent decrease in the average W–O distance of 0.05 Å from 15 to 1373 K. This apparent decrease causes the decrease in the cell edges, but it is not an actual decrease of average W–O distances. The apparent shrinkage is instead considered to be caused by the transverse thermal motion of oxygen in the Y–O–W linkages.     

Vacuum ultraviolet optical properties of (La,Gd)PO4:RE (RE=Eu, Tb)

Vacuum ultraviolet excitation spectra of phosphors (La,Gd)PO₄:RE³⁺ (RE=Eu or Tb) and X-ray photoelectron spectra of LaPO₄ and GdPO₄ are investigated. The vacuum ultraviolet excitation intensity of (La,Gd)PO₄:RE³⁺ is enhanced with the increasing of Gd³⁺ content, which implies that Gd³⁺ plays an intermediate role in energy transfer from host absorption band to RE³⁺. When Gd³⁺ is doped into LaPO₄:Eu³⁺, charge transfer band (CT band) begins to shift to higher energy region and the overlap degree of CT band and the host absorption band gets greater with more Gd³⁺ doped into LaPO₄. These results suggest that the dopant (Gd³⁺) gives an important influence on energy transfer efficiency. The top of LaPO₄ valance band is formed by the 2p level of O²⁻, whereas that of GdPO₄ valance band is formed by the 2p level of O²⁻ and the 4f level of Gd³⁺, showing the differences in band structures between LaPO₄ and GdPO₄.     

Structure and electrical conductivity of Ln2+x Hf2−x O7−x/2 (Ln = Sm-Tb; x = 0, 0.096)

Data are presented on the evolution of the pyrochlore structure in the Ln_2+x Hf_2?x O_7?δ (Ln = Sm, Eu; x = 0.096) solid solutions and Ln₂Hf₂O₇ (Ln = Gd, Tb) compounds prepared from mechanically activated oxide mixtures. Sm_2.096Hf_1.904O_6.952 is shown to undergo pyrochlore-disordered pyrochlore-pyrochlore (P-P1-P) phase transformations in the temperature range 1200–1670°C. The former transformation leads to a rise in 840°C conductivity from 10^?4 to 3 × 10^?3 S/cm in the samples synthesized at 1600°C, and the latter leads to a drop in 840°C conductivity to 6 × 10^?4 S/cm in the samples synthesized at 1670°C. The reduction in the conductivity of Sm_2.096Hf_1.904O_6.952 is accompanied by the disappearance of the assumed superstructure. In the range 1300–1670°C, Eu_2+x Hf_2?x O_7?δ (x = 0.096) and Ln₂Hf₂O₇ (Ln = Gd, Tb) have a disordered pyrochlore structure. The highest 840°C conductivity is offered by Eu_2.096Hf_1.904O_6.952, Gd₂Hf₂O₇, and Tb₂Hf₂O₇ synthesized at 1670°C: 7.5 × 10^?3, 5 × 10^?3, and 2.5 × 10^?2 S/cm, respectively.     

High porosity and low thermal conductivity high entropy (Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)C

Porous ultra-high temperature ceramics (UHTCs) are promising for ultrahigh-temperature thermal insulation applications. However, the main limitations for their applications are the high thermal conductivity and densification of porous structure at high temperatures. In order to overcome these obstacles, herein, porous high entropy (Zr_0.2Hf_0.2Ti_0.2Nb_0.2 Ta_0.2)C was prepared by a simple method combing in-situ reaction and partial sintering. Porous high entropy (Zr_0.2Hf_0.2Ti_0.2Nb_0.2Ta_0.2)C possesses homogeneous microstructure with grain size in the range of 100–500 nm and pore size in the range of 0.2–1 μm, which exhibits high porosity of 80.99%, high compressive strength of 3.45 MPa, low room temperature thermal conductivity of 0.39 W·m⁻¹ K⁻¹, low thermal diffusivity of 0.74 mm²·s⁻¹ and good high temperature stability. The combination of these properties renders porous high entropy (Zr_0.2Hf_0.2Ti_0.2Nb_0.2Ta_0.2)C promising as light-weight ultrahigh temperature thermal insulation materials.     

XRD EPR studies of ceramics Pr0.5Re0.5Ba2Cu3O7−δ in the orthorhombic and tetragonal phase

EPR, XRD, and magnetic studies are presented for Pr_0.5Re_0.5Ba₂Cu₃O_7?δ compounds (Re= La, Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm, Yb, and Lu) in the orthorhombic and tetragonal (large oxygen deficiency) phase. For the samples with Re=Dy, Ho, Y, Er, Tm, Yb, and Lu in the orthorhombic phase, the transition to the superconducting state has been observed in the temperatures rangeT _c between 18 and 40 K. For the samples with Nd and Yb in the tetragonal phase, EPR spectra coming from trivalent rare earth ions have been recorded. In the nonoxygenated sample Pr_0.5La_0.5Ba₂Cu₃O_7?δ the EPR spectrum arising from the non-Kramers trivalent praseodymium ion has been observed. A broad EPR line appearing in all our samples was attributed to superexchange interaction between copper ions over oxygen (O ₂ ^? ) bridges. Interestingly, for the Pr_0.5Re_0.5Ba_0.5Cu₃O_7?δ (Re = Er and Lu) compounds in the tetragonal phase at liquid-nitrogen temperature, a nonresonant microwave absorption in low magnetic fields has been detected.     

Superconducting and magnetic properties of ternary silicides in some rare earth-noble metal (Rh or Ir)-silicon systems

New families of ternary silicides have been prepared in the RE - Rh or Ir -Si systems and the crystal structures have been determined: RERh₃Si₂, RE₂Rh₃Si₅, RE₂RhSi₃ (RE = Y, La → Er), RERhSi (Y, La, Gd → Er), REIrSi (RE = La, Ce, Nd), RERhSi₂ and REIrSi₂ (RE = La → Gd). The RE₂RhSi₃ compounds crystallize with a new structural type, the other ones are isostructural with already known silicides or borides. Some of the silicides studied whose rare earths are diamagnetic (Y, La) show superconducting transitions above 1.6 K. They have been compared with other superconducting ternary borides, silicides, germanides and phosphides containing rare earths and noble metals. Except the phases with Y and La which are diamagnetic or show Pauli paramagnetism, the other materials order magnetically at low temperature. The onset of magnetic transitions vs. field has been observed for some compounds below 20 kOe at 4.2 K.     

Sol-Gel Synthesis and Photoluminescence of RE<Subscript>x</Subscript>Lu<Subscript>2-<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> (RE = Y,Gd) Nanophosphors

RE_xLu_2-x O₃:Eu³⁺ (RE = Y, Gd) nanophosphors with x = 0.4, 1.0, and 1.6 were synthesized using rare-earth salicylate coordination polymers as precursors for the luminescent species RE_xLu_2-x O₃:Eu³⁺ (RE = Y, Gd) composed of polyethylene glycol both as a dispersing medium and fuel. Their particle sizes were around 100 nm as determined by scanning electron microscopy and x-ray diffraction.__________From Neorganicheskie Materialy, Vol. 41, No. 6, 2005, pp. 706–710.Original English Text Copyright © 2005 by Zhou, Yan.This article was submitted by the authors in English.     

Synthesis of ternary fluorides BaCaLn2F10 - Eu2+ luminescence in BaCaLu2F10

A new family of the ternary BaCaLn₂F₁₀ (Ln=Lu, Yb, Tm, Er, Ho, Dy) system has been prepared. Emission and excitation spectra of Eu²⁺ doped BaCaLu₂F₁₀ are presented and discussed.     

Thermostability and thermoplastic formability of (Zr65Cu17.5Ni10Al7.5)100−xREx (x = 0.25–3.25, RE: Y,Gd, Tb,Dy, Ho,Er, Tm,Yb, Lu) bulk metallic glasses

The width ΔT of super-cooled liquid region (SCLR) and the softness (ΔL/L₀)_s of (Zr₆₅Cu_17.5Ni₁₀Al_7.5)_100−xRE_x (x = 0.25–3.25, rare-earth RE: Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) bulk metallic glasses (BMGs) in SCLR are systemically investigated by thermoanalysis tests, where ΔT and (ΔL/L₀)_s are used to evaluate their thermostability and thermoplastic formability in SCLR, respectively. It is found that only a small amount of Yb can be added into the matrix alloy, and the addition of each RE increases ΔT. With the addition of the same RE, (ΔL/L₀)_s depends on ΔT, but with the addition of different RE elements, (ΔL/L₀)_s and ΔT have not a clear correlation and the best addition amount is different. These phenomena and regularities are well explained based on the properties of RE elements, including boiling point, mixing enthalpy, oxides formation enthalpy and shear modulus. The improvement in the formability of (Zr₆₅Cu_17.5Ni₁₀Al_7.5)_98.00Er_2.00, which has the largest (ΔL/L₀)_s, is also verified by thermoplastic forming experiment. This composition has the best formability in the Be-free Zr-based BMGs. The researches provide a basis for development of new BMGs with better thermostability and thermoplastic formability via minor addition of RE elements.