Enzyme-Triggered Transforming of Assembly Peptide-Modified Magnetic Resonance-Tuned Probe for Highly Sensitive Imaging of Bacterial Infection In Vivo

Confirming bacterial infection at an early stage and distinguishing between sterile inflammation and bacterial infection is still highly needed for efficient treatment. Here, in situ highly sensitive magnetic resonance imaging (MRI) bacterial infection in vivo based on a peptide-modified magnetic resonance tuning (MRET) probe (MPD-1) that responds to matrix metallopeptidase 2 (MMP-2) highly expressed in bacteria-infected microenvironments is achieved. MPD-1 is an assembly of magnetic nanoparticle (MNP) bearing with gadolinium ion (Gd³⁺) modified MMP-2-cleavable self-assembled peptide (P₁) and bacteria-targeting peptide (P), and it shows T₂-weighted signal due to the assemble of MNP and MRET ON phenomenon between MNP assembly and Gd³⁺. Once MPD-1 accumulates at the bacterially infected site, P₁ included in MPD-1 is cleaved explicitly by MMP-2, which triggers the T₂ contrast agent of MPD-1 to disassemble into the monomer of MNP, leading the recovery of T₁-weighted signal. Simultaneously, Gd³⁺ detaches from MNP, further enhancing the T₁-weighted signal due to MRET OFF. The sensitive MRI of Staphylococcus aureus (low to 10⁴ CFU) at the myositis site and accurate differentiation between sterile inflammation and bacterial infection based on the proposed MPD-1 probe suggests that this novel probe would be a promising candidate for efficiently detecting bacterial infection in vivo.     

Effects of Gd doping on the sintering and microwave dielectric properties of BiNbO<Subscript>4</Subscript> ceramics

Gd³⁺ was chosen as a substitute for Bi³⁺ in BiNbO₄ ceramics, and the substitution effects on the sintering performance and microwave dielectric properties were studied in this paper. The high temperature triclinic phase was observed only in the Bi_0.98Gd_0.02NbO₄ ceramics when sintered at 920 °C. Both bulk densities and dielectric constant (ε_r) increased with the sintering temperature, while decreased with the Gd content. The quality factor (Q) exhibited a correlation to the Gd content and the microstructures of Bi_1−x Gd _x NbO₄ ceramics. At the sintering temperature of 900 °C, Bi_0.992Gd_0.008NbO₄ ceramics exhibited microwave dielectric properties of ε_r ∼ 43.87, Q × f ∼ 16,852 GHz (at 4.3 GHz), and its temperature coefficient of resonant frequency (τ_f) was found to be near-to-zero.     

Investigation on Electrical and Magnetic Properties of Gd-doped BiFeO<Subscript>3</Subscript>

Multiferroic ceramic samples of Bi_1−x Gd _x FeO₃ (x=0, 0.05, 0.1 and 0.15) have been prepared by rapid liquid-phase sintering technique. The effect of Gd substitution on ferroelectric and magnetic properties of Bi_1−x Gd _x FeO₃ ceramics has been investigated. The results of X-ray diffraction (XRD) patterns show that the single-phase BiFeO₃ sample has a rhombohedral structure and Gd³⁺ substitution for Bi³⁺ has not affected its structure. Experimental results suggest that for Bi_1−x Gd _x FeO₃ system, the ferroelectric and magnetic properties of BiFeO₃ are improved by Gd doping and the loop area increases with the Gd content. When x=0.15, saturated ferroelectric hysteresis loop is observed at room temperature with the maximal 2Pr=1.62 μC/cm², which is about 578.6% higher than that of BiFeO₃.     

Facile preparation of Gd3+ doped carbon quantum dots: Photoluminescence materials with magnetic resonance response as magnetic resonance/fluorescence bimodal probes

There are a few bimodal molecular imaging probes constructed by gadolinium (3+) ions in combination with carbon quantum dots (CQDs), and the reported ones show such obvious drawbacks as low luminous efficiency and weak MRI contrast. In the paper, a kind of CQDs photoluminescence materials with magnetic resonance response was prepared by hydrothermal method and employing gadopentetate monomeglumine (GdPM) as a precusor. Here, the GdPM plays a role of not only carbon source, but also gadolinium (3+) sources. When the GdPM aqueous solution with a concentration of 4 mg mL⁻¹ was pyrolyzed under 220 °C and 2.0 MPa for 8 h, an optimal CQDs was obtained which are doped with gadolinium (3+) ions in both chelates and Gd₂O₃ (named as Gd³⁺-CQDs). The average diameter of the Gd³⁺-CQDs is about 1.6 nm, which show a high photoluminescence quantum yield of 7.1%, as well as high longitudinal relaxivity (r₁) of 9.87 mM⁻¹ s⁻¹. And owing to the unconspicuous cell toxicity, the Gd³⁺-CQDs show big possibility for clinical application in magnetic resonance/fluorescence bimodal molecular imaging.     

Study of dielectric, magnetic and ferroelectric properties in Bi1 − xGdxFeO3

Gd-doped BiFeO₃ polycrystalline ceramics were synthesized by solid-state reaction method and their dielectric and magnetic properties were investigated. X-ray diffraction pattern showed that Bi_1 − xGd_xFeO₃ (x = 0, 0.05 and 0.1) ceramics were rhombohedral. The Gd substitution has suppressed the usual impurity peaks present in the parent compound and we obtained single phase Bi_0.9Gd_0.1FeO₃ ceramic. Gd substitution reduced the antiferromagnetic Néel temperature (T_N) in Bi_1 − xGd_x FeO_3. An anomaly in the dielectric constant(ε) and dielectric loss(tan (δ)) in the vicinity of the antiferromagnetic Néel temperature (T_N) was observed. Ferroelectric and magnetic hysteresis loops measured at room temperature indicated the coexistence of ferroelectricity and magnetism. The room temperature magnetic hysteresis loops were not saturated, but the magnetic moment was found to increase with increase in Gd concentration.     

Synthesis and properties of Ce1−xGdxO2−x/2 solid solution prepared by flame spray pyrolysis

Flame spray pyrolysis, which produces ultrafine particles, was applied to the synthesis of Ce_1−xGd_xO_2−x/2 solid solutions by substituting Gd from a mole fraction of 0–0.40. The solubility limit of Gd in the Ce_1−xGd_xO_2−x/2 solid solution produced by flame spray pyrolysis was between 0.25 and 0.30, which is consistent with the reported value. The as-prepared Ce_1−xGd_xO_2−x/2 particles had a square morphology and a nanometer range in the equivalent diameter. The small particle size made it possible to reduce the sintering temperature of the Ce_1−xGd_xO_2−x/2 solid solution from 1650 °C to 1400 °C for the ceria-based solid electrolytes produced by the solid state preparation. The maximum ionic conductivity was achieved when the mole fraction of Gd was 0.25. The mole fraction for the highest ionic conductivity was the same as the particles produced by hydrothermal synthesis. However, the ionic conductivity of the Ce_1−xGd_xO_2−x/2 prepared by the flame spray pyrolysis (1.01 × 10⁻² S/cm at 600 °C) was higher than that prepared by the hydrothermal synthesis (7.53 × 10⁻³ S/cm at 600 °C).     

The Effect of Gd Concentration on the Physical and Magnetic Properties of Bi1.7Pb0.3-xGdxSr2Ca3Cu4O12+y Superconductors

Bi–Pb–Gd–Sr–Ca–Cu–O bulk samples with nominal composition Bi_1.7Pb _0.3-xGd_xSr₂Ca₃Cu₄O_12+y (x=0.01, 0.05, 0.075, 0.10) were prepared by the melt-quenching method. The effects of different Gd doping on the structure have been investigated by electrical resistance, scanning electron micrographs, XRD, magnetization and magnetic hysteresis loop measurements. The magnetization measurements have been carried out as a function of magnetic field for fields up to 5 kOe at temperatures well below the zero resistance temperatures of the annealed samples. It has been found that the high-T_c superconducting phase, (2 2 2 3), is formed in the sample A with concentration x = 0.01, annealed at 840°C for 120 h. However, with increasing Gd³⁺ doping for Pb²⁺ the (2 2 2 3) phase gradually transforms into the (2 2 1 2) phase. The magnitudes of magnetization and initial susceptibility, | M | and | dM/dH|, and the hysteresis loop areas decrease with increasing Gd concentration x and/or temperature T. The fast decreases in | M|, | dM/dH |, and the hysteresis loop areas related to the superconducting volume, with increasing x and/or T seem to imply an existence of flux pinning centres in our samples. In order to support this implication the critical current densities J_c, of the samples, have been estimated at two fixed temperatures, 9 and 30 K. Our data have indicated that J_c decreases with increasing temperature and/or Gd concentration, as expected.     

High-Performance,Light-Stimulation Healable,and Closed-Loop Recyclable Lignin-Based Covalent Adaptable Networks

In this work, high-performance, light-stimulation healable, and closed-loop recyclable covalent adaptable networks are successfully synthesized from natural lignin-based polyurethane (LPU) Zn²⁺ coordination structures (LPUxZy). Using an optimized LPU (LPU-20 with a tensile strength of 28.4 ± 3.5 MPa) as the matrix for Zn²⁺ coordination, LPUs with covalent adaptable coordination networks are obtained that have different amounts of Zn. When the feed amount of ZnCl₂ is 9 wt%, the strength of LPU-20Z9 reaches 37.3 ± 3.1 MPa with a toughness of 175.4 ± 4.6 MJ m⁻³, which is 1.7 times of that of LPU-20. In addition, Zn²⁺ has a crucial catalytic effect on “dissociation mechanism” in the exchange reaction of LPU. Moreover, the Zn²⁺-based coordination bonds significantly enhance the photothermal conversion capability of lignin. The maximum surface temperature of LPU-20Z9 reaches 118 °C under the near-infrared illumination of 0.8 W m⁻². This allows the LPU-20Z9 to self-heal within 10 min. Due to the catalytic effect of Zn²⁺, LPU-20Z9 can be degraded and recovered in ethanol completely. Through the investigation of the mechanisms for exchange reaction and the design of the closed-loop recycling method, this work is expected to provide insight into the development of novel LPUs with high-performance, light-stimulated heal ability, and closed-loop recyclability; which can be applied toward the expanded development of intelligent elastomers.     

The magnetocaloric effect in (Gd0.74Tb0.26)5(SixGe1−x)4 alloys

The magnetic phase transition and magnetocaloric effect of the alloys of Gd_0.74Tb_0.26 and (Gd_0.74Tb_0.26)₅(Si_xGe_1−x)₄ (x = 0.43, 0.50, 0.505) have been investigated by magnetization measurement. Experimental results show that partial substitution of the Gd by Tb in Gd₅(Si_xGe_1−x)₄ system keeps the first order magnetic transition. Although the values of transition temperature decrease, the as-cast (Gd_0.74Tb_0.26)₅(Si_0.43Ge_0.57)₄ and annealed (Gd_0.74Tb_0.26)₅(Si_0.50Ge_0.50)₄ alloys display large magnetic entropy change up to 18.89 J kg^− 1 K^− 1 and 13.79 J kg^− 1 K^− 1 near their transition temperatures in the low magnetic field change of 0–2.0 T, respectively.     

Crystal growth and characterization of Tm doped mixed rare-earth aluminum perovskite

In this work, we present results of structural characterization and optical properties including radio luminescence of (Lu_xGd_yY_0.99?x?yTm_0.01)AP single crystal scintillators for (x, y) = (0.30, 0.19), (0, 0.19) and (0, 0) grown by the micro-pulling-down (μ-PD) method. The grown crystals were single phase materials with perovskite structure (Pbnm) as confirmed by XRD and had a good crystallinity. The distribution of the crystal constituents in growth direction was evaluated, and significant segregation of Lu and Gd was detected in (Lu_0.30Gd_0.19Y_0.50Tm_0.01)AP sample. The crystals demonstrated 70% transmittance in visible wavelength range and some absorption bands due to Tm³⁺, Gd³⁺ and color centers were exhibited in 190–900 nm. The radioluminescence measurement under X-ray irradiation demonstrated several emission peaks ascribed to 4f–4f transitions of Tm³⁺ and Gd³⁺. The ratio of emission intensity in longer wavelength range was increased when Y was replaced by Lu or Gd.     

Shaped single crystal growth and scintillating application of Yb:(Gd,Lu)3(Ga,Al)5O12 solid solutions

Shaped single crystals of (Yb_0.05Lu_xGd_0.95−x)Ga₅O₁₂ (0.0x0.9) and Yb_0.15Gd_0.15Lu_2.7(Al_xGa_1−x)O₁₂ (0.0x1.0) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃(Ga,Al)₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect––host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

Tantalum influence on electrical properties of lead-free (K0.4425Na0.52Li0.0375)(Nb0.93?xTaxSb0.07) O3 piezoelectric ceramics

Lead-free (K_0.4425Na_0.52Li_0.0375)(Nb_0.93−x Sb_0.07Ta _x )O₃ (abbreviated as KNLNST _x ) piezoelectric ceramics with x = 0.045–0.075 have been prepared by an ordinary sintering technique with sintering temperature at 1,120 °C. The results of X-ray diffraction reveal that Ta⁵⁺ has diffused into the perovskite lattice to form a solid solution. The grain growth of the ceramics was inhibited by substituting Ta⁵⁺ for Nb⁵⁺. It has been shown that the substitution of Ta decreases Curie temperature T _C and orthorhombic-tetragonal phase transition temperature T _O-T. Besides, the dependence of the ceramics with different Ta content on the dielectric, piezoelectric and ferroelectric properties has been investigated. The results indicate that Ta substitution provides “soft” piezoelectric characteristics, owing to improvements in d ₃₃, k _p and ε _r and a decease in Q _m. For the ceramics with x = 0.06, the piezoelectric coefficient d ₃₃ becomes maximum at a value of 270 pC/N, while the other electrical properties remain reasonably high: dielectric constant ε _r = 1,577, planar mode electromechanical coupling factors k _p = 0.4, Curie temperature T _C = 252 °C and the remanent polarization P _r = 16.03 μC/cm². These results show that (K, Na, Li) (Nb, Sb)O₃ ceramics with small amount of Ta (x <8 mol%) are good lead-free piezoelectric ceramic.     

Emission (Gd3+ and Sm3+) and ESR (Gd3+) studies of La1−xLnxB3O6 (Ln = Gd,Sm; 0 ≤ x ≤ 0.2 for Gd; 0 ≤ x ≤ 0.1 for Sm) phosphors

Polycrystalline powders of rare-earth doped La_1?xGd_xB₃O₆ (0?≤?x?≤?0.2) and La_1?xSm_xB₃O₆ (0.0?≤?x?≤?0.1) phosphors were successfully prepared by a B₂O₃ flux method. All the phosphor samples are well characterized by powder X-ray diffraction (XRD), infrared (IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) methods and fluorescence lifetime of Sm³⁺ ion. The XRD patterns show that La_1?xM_xB₃O₆ (M?=?Gd and Sm) adopt monoclinic with the I2/a space group. The SEM–EDS results confirmed the doping of Gd and Sm into LaB₃O₆ lattice. The IR and Raman spectra of these solid solutions gave distinctive bands corresponding to planar BO₃ and tetrahedral BO₄ groups. The photoluminescence (PL) spectra of La_1?xGd_xB₃O₆ gave a strong emission band, ⁶P_J?→?⁸S_7/2, at 310 nm. The PL spectra of La_1?xSm_xB₃O₆ phosphor showed orange-red emission at 598 nm when excited using light of wavelength of 402 nm. The results were obtained by the transition ⁴G_5/2?→?⁶H_7/2 of Sm³⁺ ions. The influence of dopant concentration on the emission profiles was studied. The ESR spectra of La_1?xGd_xB₃O₆ (x?=?0.02) gave a typical U-spectrum and spin-Hamiltonian parameters are deduced.

     

Exceedingly Small Gadolinium Oxide Nanoparticles with Remarkable Relaxivities for Magnetic Resonance Imaging of Tumors

Gd chelates have occupied most of the market of magnetic resonance imaging (MRI) contrast agents for decades. However, there have been some problems (nephrotoxicity, non‐specificity, and low r₁) that limit their applications. Herein, a wet‐chemical method is proposed for facile synthesis of poly(acrylic acid) (PAA) stabilized exceedingly small gadolinium oxide nanoparticles (ES‐GON‐PAA) with an excellent water dispersibility and a size smaller than 2.0 nm, which is a powerful T₁‐weighted MRI contrast agent for diagnosis of diseases due to its remarkable relaxivities (r₁ = 70.2 ± 1.8 mM^?1 s^?1, and r₂/r₁ = 1.02 ± 0.03, at 1.5 T). The r₁ is much higher and the r₂/r₁ is lower than that of the commercial Gd chelates and reported gadolinium oxide nanoparticles (GONs). Further ES‐GON‐PAA is developed with conjugation of RGD2 (RGD dimer) (i.e., ES‐GON‐PAA@RGD2) for T₁‐weighted MRI of tumors that overexpress RGD receptors (i.e., integrin α_vβ₃). The maximum signal enhancement (ΔSNR) for T₁‐weighted MRI of tumors reaches up to 372 ± 56% at 2 h post‐injection of ES‐GON‐PAA@RGD2, which is much higher than commercial Gd‐chelates (<80%). Due to the high biocompatibility and high tumor accumulation, ES‐GON‐PAA@RGD2 with remarkable relaxivities is a promising and powerful T₁‐weighted MRI contrast agent.     

Ten‐Gram‐Scale Facile Synthesis of Organogadolinium Complex Nanoparticles for Tumor Diagnosis

The market of available contrast agents for clinical magnetic resonance imaging (MRI) has been dominated by gadolinium (Gd) chelates based T₁ contrast agents for decades. However, there are growing concerns about their safety because they are retained in the body and are nephrotoxic, which necessitated a warning by the U.S. Food and Drug Administration against the use of such contrast agents. To ameliorate these problems, it is necessary to improve the MRI efficiency of such contrast agents to allow the administration of much reduced dosages. In this study, a ten‐gram‐scale facile method is developed to synthesize organogadolinium complex nanoparticles (i.e., reductive bovine serum albumin stabilized Gd‐salicylate nanoparticles, GdSalNPs‐rBSA) with high r₁ value of 19.51 mm ^?1 s^?1 and very low r₂/r₁ ratio of 1.21 (B₀ = 1.5 T) for high‐contrast T₁‐weighted MRI of tumors. The GdSalNPs‐rBSA nanoparticles possess more advantages including low synthesis cost (≈0.54 USD per g), long in vivo circulation time (t_1/2 = 6.13 h), almost no Gd³⁺ release, and excellent biosafety. Moreover, the GdSalNPs‐rBSA nanoparticles demonstrate excellent in vivo MRI contrast enhancement (signal‐to‐noise ratio (ΔSNR) ≈ 220%) for tumor diagnosis.     

Phase structure evolution and chemical durability studies of Gd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Yb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> ceramics for immobilization of minor actinides

Rare earth phosphates (REPO₄) are considered as promising materials to immobilize the high-level radioactive waste. In the paper, Gd_1?xYb _x PO₄ (x = 0, 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0) series were prepared via the solid-state reaction using Gd as the surrogate for minor actinide Am and Cm, and the structure, phase transformation and morphology were characterized by XRD, Raman, TEM and SEM. With the calcination temperature ranging from 1200 to 1500 °C, the coexisted phases of monazite- and xenotime-type structure are observed in Gd_0.9Yb_0.1PO₄. The monophasic xenotime-type Gd_0.9Yb_0.1PO₄ is obtained at 1600 °C. The monazite → xenotime transformation of Gd_1?xYb _x PO₄ depends on the substitution of Gd³⁺ by Yb³⁺ ions. With the decrease in Gd³⁺ content, the gradual changes of FWHM and the hypsochromic shift of P-O symmetrical stretching vibration (Vs) are observed in the Raman spectra, indicating that the distortion of PO₄ tetrahedra occurs during the phase transformation process. The chemical durability test is measured by the ASTM product consistency test leaching method, and the normalized mass loss (NL_Gd) of Gd and (NL_Yb) of Yb is extremely low and shown in the order of 10^?6–10^?7 g/m² for all the ceramics.     

Spin Gap Characteristic of Y(Ba1?xGdx)2Cu3O7?δ

Y(Ba_1–x Gd _x )₂Cu₃O_7– compounds with x = 0 0.15 are prepared using the solid reaction technique. With structure analysis by Rietveld refinement of x-ray diffraction, we find that Gd³⁺ ions prefer to occupy Y sites within lighter doping x 0.08 due to ion size effects, then begin partially to occupy Ba sites with doping content increasing, which gives vital influence on superconductivity and spin-gap properties. The magnetic doping effects of Gd³⁺ ions on spin-gap properties are investigated in detail by contrast of the distinguished behaviors between T* and T _c, indicating that spin-gap temperature is not completely determined by the carrier density, but strongly dependent on the strength of interplane antiferromagnetic coupling. Finally, we propose an expression of in-plane resistivity dependent on the maximal width of spin-gap ₀ to derive their values for different samples, which almost keep constant with the increase of Gd doping contents.     

Enhanced Piezoelectric,Ferroelectric, and Electrostrictive Properties of Lead-Free (1-x)BCZT-(x)BCST Electroceramics with Energy Harvesting Capability

Next-generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)-free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi-phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead-free piezoelectric materials (1-x)Ba_0.95Ca_0.05Ti_0.95Zr_0.05O₃-(x)Ba_0.95Ca_0.05Ti_0.95Sn_0.05O₃, are reported, which are represented as (1-x)BCZT-(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1-x)BCZT-(x)BCST materials are synthesized by high-temperature solid-state ceramic reaction method by varying x in the full range (x = 0.00–1.00). In-depth exploration research is performed on the structural, dielectric, ferroelectric, and electro-mechanical properties of (1-x)BCZT-(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X-ray diffraction (XRD) analyses, which also reveals that the Ca²⁺, Zr⁴⁺, and Sn⁴⁺ are well dispersed within the BaTiO₃ lattice. For all (1-x)BCZT-(x)BCST ceramics, thorough investigation of phase formation and phase-stability using XRD, Rietveld refinement, Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and temperature-dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2 + P4mm) phases at room temperature. The steady transition of Amm2 crystal symmetry to P4mm crystal symmetry with increasing x content is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral-orthorhombic (T_R-O), orthorhombic- tetragonal (T_O-T), and tetragonal-cubic (T_C), gradually shift toward lower temperature with increasing x content. For (1-x)BCZT-(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constant ε_r ≈ 1900–3300 (near room temperature), ε_r ≈ 8800–12 900 (near Curie temperature), dielectric loss, tan δ ≈ 0.01–0.02, remanent polarization P_r ≈ 9.4–14 µC cm⁻², coercive electric field E_c ≈ 2.5–3.6 kV cm⁻¹. Further, high electric field-induced strain S ≈ 0.12–0.175%, piezoelectric charge coefficient d₃₃ ≈ 296–360 pC N⁻¹, converse piezoelectric coefficient ${(d_{33}^{\ast })}_{\mathrm{ave}}$≈ 240–340 pm V⁻¹, planar electromechanical coupling coefficient k_p ≈ 0.34–0.45, and electrostrictive coefficient (Q₃₃)_avg ≈ 0.026–0.038 m⁴ C⁻² are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT-(0.4)BCST composition (x = 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead-free piezoelectric (1-x)BCZT-(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1-x)BCZT-(x)BCST ceramics as a potentially strong contender within the family of Pb-free piezoelectric materials for future electronics and energy harvesting device technologies.     

High–temperature phase chemistry of the system Gd–Pd–O

Anisothermal sectionof the phase diagram for the system Gd–Pd–O at 1223 K has been established by equilibrationof samples and phase identification after quenching by optical and scanning electron microscopy, X–ray powder diffraction, and energy dispersive spectroscopy. Three ternary oxides Gd₄PdO₇,Gd₂PdO₄ and Gd₂Pd₂O₅ were identified. Liquid alloys, the four inter–metallic compounds and Pd–rich solid solutionwere found to be inequilibrium with Gd₂O₃.

Based on the phase relations, four solid–state cells were designed to measure the Gibbs energies of formation of the three ternary oxides in the temperature range from 920 to 1320 K. Although three cells are sufficient to obtain the properties of the three compounds, the fourth cell was deployed to cross check the data. An advanced version of the solid–state cell incorporating a buffer electrode with yttria–stabilized zirconia solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode was used for high–temperature thermodynamic measurements. The standard Gibbs energy of formation of the inter–oxide compounds from their component binary oxides can be represented by the following equations:

Gd₄PdO₇(s) : Δ_f(ox)G⁰/J mol^–1 = –25,030 + 0.33T (±140), Gd₂PdO₄(s) : Δf(ox)_f(ox)G⁰/J mol^–1 = –25,350 + 0.84T (±135), Gd₂Pd₂O₅(s) : Δf(ox)_f(ox)G⁰/J mol^–1 = –48,700 + 0.38T (±270)

Based on the thermodynamic information, isothermal chemical potential diagrams and isobaric phase diagrams for the system Gd–Pd–O are developed.     

Effect of gadolinium ions on the structure and magnetic properties of zinc-borate glasses and glass ceramics

X-ray diffraction (XRD), electron paramagnetic resonance (EPR), and magnetic susceptibility measurements have been employed to investigate the samples from the (Gd₂O₃) _x ·(B₂O₃)_(60−x)·(ZnO)₄₀ (0 ≤ x ≤ 20 mol%) system. The XRD pattern for the prepared samples shows that the vitreous phase is present only for x ≤ 15 mol%. For the samples containing 20 mol% Gd₂O₃ the presence of a unique crystalline phase, GdBO₃, embedded in a vitreous matrix was evidenced. In this case the XRD patterns show the presence of nanometer sized crystals (64 nm) in a glassy matrix. The EPR spectra of the studied samples exhibit three important features with effective g-values of ≈6, 2.8, 2.0 and a weaker feature at g ≈ 4.8. For low Gd₂O₃ contents (x < 3 mol%), the EPR spectra have the typical ‘‘U’’-type shape. For higher contents of Gd₂O₃ (x ≥ 3 mol%), the spectral features are broadened and finally are dominated by a single broad absorption line located at g ≈ 2.0. This broad EPR line is associated to the Gd³⁺ ions present predominantly as clustered species. Magnetic susceptibility data show that for x > 1 mol% the Gd³⁺ ions are present not only as isolated species but also as species coupled through antiferromagnetic exchange interactions.