Novel Sol-Gel Synthesis Route for Ce- and V-Doped Ba0.85Ca0.15Ti0.9Zr0.1O3 Piezoceramics.

To meet the current demand for lead-free piezoelectric ceramics, a novel sol-gel synthesis route is presented for the preparation of Ba0.85Ca0.15Ti0.9Zr0.1O3 doped with cerium (Ce = 0, 0.01, and 0.02 mol%) and vanadium (V = 0, 0.3, and 0.4 mol%). X-ray diffraction patterns reveal the formation of a perovskite phase (space group P4mm) for all samples after calcination at 800 °C and sintering at 1250, 1350, and 1450 °C, where it is proposed that both dopants occupy the B site. Sintering studies show that V doping allows the sintering temperature to be reduced to at least 1250 °C. Undoped BCZT samples sintered at the same temperature show reduced functional properties compared to V-doped samples, i.e., d33 values increase by an order of magnitude with doping. The dissipation factor tan δ decreases with increasing sintering temperature for all doping concentrations, while the Curie temperature TC increases for all V-doped samples, reaching 120 °C for high-concentration co-doped samples. All results indicate that vanadium doping can facilitate the processing of BCZT at lower sintering temperatures without compromising performance while promoting thermal property stability.

Synthesis and high-frequency magnetoelectric characterization of the 0-3 particulate lead-free multiferroic composite KNN/CFO.

The research for lead-free magnetoelectric (ME) multiferroic composite materials has increased considerably because they are environmentally friendly. For composites with 0-3 connectivity, synthesis with lead-free phase has proven challenging to obtain high values of ME coupling. This work reports the successful synthesis of the KNN/CFO composite (K0.5N0.5NbO3/CoFe2O4) by conventional synthesis process. XRD and SEI showed two well-defined, also presenting good electric polarization values. The ME coefficient was very high, reaching values close to 2850 mV cm-1·Oe at the electromechanical resonance frequency. The dipolar interaction between the electric charges and magnetic moments of the KNN and CFO phases was responsible for the high value and the behavior of dependence on the applied magnetic field.

Advancements and Prospects in Perovskite Solar Cells: From Hybrid to All-Inorganic Materials.

Hybrid perovskites, materials composed of metals and organic substances in their structure, have emerged as potential materials for the new generation of photovoltaic cells due to a unique combination of optical, excitonic and electrical properties. Inspired by sensitization techniques on TiO2 substrates (DSSC), CH3NH3PbBr3 and CH3NH3PbI3 perovskites were studied as a light-absorbing layer as well as an electron-hole pair generator. Photovoltaic cells based on per-ovskites have electron and hole transport layers (ETL and HTL, respectively), separated by an ac-tive layer composed of perovskite itself. Major advances subsequently came in the preparation methods of these devices and the development of different architectures, which resulted in an efficiency exceeding 23% in less than 10 years. Problems with stability are the main barrier to the large-scale production of hybrid perovskites. Partially or fully inorganic perovskites appear promising to circumvent the instability problem, among which the black perovskite phase CsPbI3 (α-CsPbI3) can be highlighted. In more advanced studies, a partial or total substitution of Pb by Ge, Sn, Sb, Bi, Cu or Ti is proposed to mitigate potential toxicity problems and maintain device efficiency.

Development of Lead-Free Radiation Shielding Material Utilizing Barium Sulfate and Magnesium Oxide as Fillers in Addition Cure Liquid Silicone Rubber.

The radiological protection has the purpose of safeguarding the physical well-being of the user, preventing exposure to detrimental levels of ionizing radiation. This study introduces a novel, cost-effective category of lead-free elastomeric material designed for radiation shielding. The filler compounds utilized are notably lighter than conventional lead-based materials, enhancing user ergonomics during application. They comprise of a blend of barium sulfate combined or not with magnesium oxide with addition-cure liquid silicone rubber. To ensure the effectiveness of the radiation shielding, X-ray transmission measurements were performed for the different thicknesses of the materials and the results compared with Monte Carlo simulations. Additionally, the physical properties of the new materials, such as density, homogeneity, tensile strength, viscosity, and wettability, were also evaluated. The findings indicate that both materials fulfill the requirement for application in radiation protection garments.

Structural Characterization and Thermoelectric Properties of Br-Doped AgSnm[Sb0.8Bi0.2]Te2+m Systems.

Herein, we report the synthesis, structural and microstructural characterization, and thermoelectric properties of AgSnm[Sb0.8Bi0.2]Te2+m and Br-doped telluride systems. These compounds were prepared by solid-state reaction at high temperature. Powder X-ray diffraction data reveal that these samples exhibit crystal structures related to the NaCl-type lattice. The microstructures and morphologies are investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDS), and high-resolution transmission electron microscopy (HRTEM). Positive values of the Seebeck coefficient (S) indicate that the transport properties are dominated by holes. The S of undoped AgSnm[Sb0.8Bi0.2]Te2+m ranges from +40 to 57 µV·K-1. Br-doped samples with m = 2 show S values of +74 µV·K-1 at RT, and the Seebeck coefficient increases almost linearly with increasing temperature. The total thermal conductivity (κtot) monotonically increases with increasing temperature (10-300 K). The κtot values of undoped AgSnm[Sb0.8Bi0.2]Te2+m are ~1.8 W m-1 K-1 (m = 4) and ~1.0 W m-1 K-1 (m = 2) at 300 K. The electrical conductivity (σ) decreases almost linearly with increasing temperature, indicating metal-like behavior. The ZT value increases as a function of temperature. A maximum ZT value of ~0.07 is achieved at room temperature for the Br-doped phase with m = 4.

Ferroelectric, Dielectric and Electromechanical Performance of Ba0.92Ca0.08Ti0.95Zr0.05O3 Ceramics with an Enhanced Curie Temperature.

Ba0.92Ca0.08Ti0.95Zr0.05O3 (BCZT8-5) ceramic materials have been scarcely studied as lead-free piezo/ferroelectrics despite their enhanced Curie temperature (>100 °C) with respect to most studied BCZT compositions. In this work, homogeneous dense BCZT8-5 ceramics with grain size in the range of 20 µm, and optimum ferroelectric, dielectric, and electromechanical performance, were prepared by the mixed oxides route using moderate synthesis (1250 °C-2 h) and sintering (1400 °C-2 h) conditions. Thickness-poled thin disks and monomodal shear plate resonators were used for the determination of piezoelectric coefficients, coupling factors, elastic, and dielectric permittivity coefficients, including all losses, by iterative analysis of impedance curves at resonance. Furthermore, the thermal evolution of the piezoelectric characteristics at resonance was determined to assess the enhanced working range of the ceramics (≈100 °C). Ferroelectric hysteresis loops and strains vs. electric-field butterfly loops were also measured and showed soft behavior with Ec = 2 kV/cm, Pr = 12 µC/cm2 after a maximum applied field of 3 kV was used. The ceramics showed a high endurance of P-E cycles to electrical fatigue up to 107 cycles. Moreover, dielectric properties as a function of temperature were also accomplished and showed nearly normal ferroelectric behavior, characteristic of samples with low crystallographic disorder. Overall, these ceramics showed high sensitivity and higher stability than other currently studied BCZT compositions.

Preparation of Heterojunctions Based on Cs3Bi2Br9 Nanocrystals and g-C3N4 Nanosheets for Photocatalytic Hydrogen Evolution.

Heterojunctions based on metal halide perovskites (MHPs) are promising systems for the photocatalytic hydrogen evolution reaction (HER). In this work, we coupled Cs3Bi2Br9 nanocrystals (NCs), obtained by wet ball milling synthesis, with g-C3N4 nanosheets (NSs), produced by thermal oxidation of bulk g-C3N4, in air. These methods are reproducible, inexpensive and easy to scale up. Heterojunctions with different loadings of Cs3Bi2Br9 NCs were fully characterised and tested for the HER. A relevant improvement of H2 production with respect to pristine carbon nitride was achieved at low NCs levels reaching values up to about 4600 µmol g-1 h-1. This work aims to provide insights into the synthesis of inexpensive and high-performing heterojunctions using MHP for photocatalytic applications.

Lead-Free Metal Halide Perovskite Nanocrystals: From Fundamentals to Applications.

Lead (Pb) halide perovskite nanocrystals, with the general formula APbX3 , where A=CH3 NH3+ , CH(NH2 )2+ , or Cs+ and X=Cl- , Br- , or I- , have emerged as a class of materials with promising properties due to their remarkable optical properties and solar cell performance. However, important issues still need to be addressed to enable practical applications of these materials, such as instability, mass production, and Pb toxicity. Recent studies have carried out the replacement of Pb by various less-toxic cations as Sn, Ge, Sb, and Bi. This variety of chemical compositions provide Pb-free perovskite and metal halide nanostructures with a wide spectral range, in addition to being considered less toxic, therefore having greater practical applicability. Highlighting the necessity to address and solve the toxicity problems related to Pb-containing perovskite, this review considers the prospects of the Pb-free perovskite, involving synthesis methods, and properties of them, including advantages, disadvantages, and applications.

Lead Levels in a Potters Population and Its Association With the Use of Different Glazes: Cross-Sectional Evaluation of the Approved Pottery Program.

Lead is one of the most harmful toxic metals to humans. In Mexico, though most potters still use a lead-based glazing process, a new lead-free glaze has been introduced to the production of pottery. The Approved Pottery Program (APP) promotes the production of lead-free pottery. As a component of the APP, we aimed to document in this pilot study the blood lead levels (BLLs) of a sample of potters and the association with the type of glaze used. A cross-sectional study was conducted based on information from 46 potters grouped by 26 workshops. We measured general sociodemographic characteristics, capillary BLLs, and the lead levels of the dirt floors of the workshops. The evaluation of associations and comparisons between glaze types was performed based on a regression model clustered by workshop. The median BLL measured was 13.6 µg/dl (IQR: 7.8-20.4 µg/dl), and 70% of the BLLs were greater than 10 µg/dl. Workshop managers presented higher BLLs compared to others working in the same workshop (median of 14.1 µg/dl (IQR: 11.6-25.3 µg/dl) versus 10.1 µg/dl (IQR: 5.2-16.7 µg/dl), respectively). The median BLLs of potters who used lead-free glaze in at least 80% of production were 8.8 µg/dl (95% CI: -17.3 to -0.3 µg/dl) lower than the BLLs of those who used lead-free glaze in less than 30% of production, adjusted by workshop role. Additionally, the lead levels were significantly lower in workshop dirt floors where lead-free glaze was used in at least 80% of the production compared to those that use less than 30% (180 versus 916 mg/kg; p < 0.05). The use of lead-free glaze in the production of pottery was associated with both lower BLLs in potters and lower soil lead levels in the workshop area.

Selection and Optimization of a K0.5Na0.5NbO3-Based Material for Environmentally-Friendly Magnetoelectric Composites.

Li- and Ta-modified K 0.5 Na 0.5 NbO 3 compounds are among the most promising lead-free ferroelectrics for high-sensitivity piezoelectric ceramic materials, and are potentially capable of replacing Pb(Zr,Ti)O 3 . They are also being investigated as piezoelectric components in environmentally friendly magnetoelectric composites. However, most suitable modifications for this application have not been identified. We report here a simulation study of how the magnetoelectric voltage responses of layered composite structures based on Li x (K 0.5 Na 0.5 ) 1 - x Nb 1 - y Ta y O 3 varies with the chemical composition of the piezoelectric. Instead of relying on material coefficients from the literature, which would have required using different sources, an ad hoc set of materials was prepared. This demanded tailoring preparation by conventional means to obtain dense ceramics while controlling alkali volatilization, perovskite phase and microstructure, as well as characterizing their dielectric, elastic and electromechanical properties. This provided the set of relevant material coefficients as a function of composition, which was used to obtain the magnetoelectric responses of model layered structures including a reference magnetostrictive spinel oxide by simulation. The piezoelectric material leading to the highest magnetoelectric coefficient was identified, and shown to be different to that showing the highest piezoelectric coefficient. This reflects the dependence of the magnetoelectric response on all material coefficients, along with the complex interplay between composition, processing and properties in K 0.5 Na 0.5 NbO 3 -based ceramics.

Analysis of Luminescent Gunshot Residue (LGSR) on Different Types of Fabrics.

The collection of gunshot residue on fabric can be an arduous task due to the microscopic size of particles (blind collection) and sheddability of some fabrics. The introduction of luminescent markers and consequent formation of luminescent gunshot residue (LGSR) can facilitate this analysis. In this study, different fabrics were analyzed in order to verify the persistence of the LGSR on them, the possibility of collecting and analyzing particles by video spectral comparator (VSC) and SEM/EDS. Also, different colored fabrics were used as targets in order to investigate influence of fabric color on LGSR visualization. Furthermore, the influence of the fabric type in the distribution of the LGSR deposited around the projectile´s hole entrance was evaluated. The fabric sheddability did not alter collection of the particles or analysis. It was possible to observe and collect LGSR on all tested fabrics, even after the fabric had been shaken, or in colored fabrics.

Use of luminescent gunshot residues markers in forensic context-Part II.

Gunshot residues (GSR) are important physical evidence in firearm-related crimes. Recently developed non-toxic ammunition, however, requires a new methodology for its characterization. To overcome this drawback, the introduction of noncommercial luminescent markers in ammunition was proposed. These markers, synthesized and added to the gunpowder, presented as a versatile tool for GSR analysis, since they require UV radiation alone to visualize the luminescent GSR (LGSR). This has opened up new perspectives for understanding GSR behavior at a crime scene. This work aims to expand previous studies performed with the luminescent markers in forensic contexts, exploring four different important aspects related to GSR behavior. Using LGSR amount/dispersion and a series of blind tests with marked ammunition, we tried to (1) identify the shooter position; (2) estimate the shooting distance; (3) evaluate the influence of the pistol type on the LGSR distribution on the shooter's hands and guns; and (4) study the transference of LGSR by a chain of handshaking. For this purpose, a portable UV lamp (λ=254nm) and/or techniques such as video spectral comparator (VSC) and scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDS) were used to visualize and analyze the residues. As a result, the observation of the LGSR enabled accurate determination of the shooter position and the firing distance without any chemicals. Besides, the LGSR were visualized on different kinds of pistols, regardless of firing mechanism. And finally, this study evidenced transference of residues from shaking hands with the shooter, which should be carefully considered when interpreting the results of a GSR analysis.

Piezoelectric Ceramics of the (1 - x)Bi0.50Na0.50TiO3-xBa0.90Ca0.10TiO3 Lead-Free Solid Solution: Chemical Shift of the Morphotropic Phase Boundary, a Case Study for x = 0.06.

Research and development of lead-free piezoelectric materials are still the hottest topics in the field of piezoelectricity. One of the most promising lead-free family of compounds to replace lead zirconate-titanate for actuators is that of Bi0.50Na0.50TiO3 (BNT) based solid solutions. The pseudo-binary (1 - x)Bi0.50Na0.50TiO3-xBa1 - yCayTiO3 system has been proposed for high temperature capacitors and not yet fully explored as piezoelectric material. In this work, the solid solution with x = 0.06 and y = 0.10 was obtained by two different synthesis routes: solid state and Pechini, aiming at using reduced temperatures, both in synthesis (<800 °C) and sintering (<1150 °C), while maintaining appropriated piezoelectric performance. Crystal structure, ceramic grain size, and morphology depend on the synthesis route and were analyzed by X-ray diffraction, together with scanning and transmission electron microscopy. The effects of processing and ceramic microstructure on the structural, dielectric, ferroelectric, and piezoelectric properties were discussed in terms of a shift of the Morphotropic Phase Boundary, chemically induced by the synthesis route.

Compositional Design of Dielectric, Ferroelectric and Piezoelectric Properties of (K, Na)NbO3 and (Ba, Na)(Ti, Nb)O3 Based Ceramics Prepared by Different Sintering Routes.

Lead free piezoelectric materials are being intensively investigated in order to substitute lead based ones, commonly used in many different applications. Among the most promising lead-free materials are those with modified NaNbO3, such as (K, Na)NbO3 (KNN) and (Ba, Na)(Ti, Nb)O3 (BTNN) families. From a ceramic processing point of view, high density single phase KNN and BTNN ceramics are very difficult to sinter due to the volatility of the alkaline elements, the narrow sintering temperature range and the anomalous grain growth. In this work, Spark Plasma Sintering (SPS) and high-energy ball milling (HEBM), following heat treatments (calcining and sintering), in oxidative (O2) atmosphere have been used to prepare single phase highly densified KNN ("pure" and Cu2+ or Li1+ doped), with theoretical densities ρth > 97% and BTNN ceramics (ρth - 90%), respectively. Using BTTN ceramics with a P4mm perovskite-like structure, we showed that by increasing the NaNbO3 content, the ferroelectric properties change from having a relaxor effect to an almost "normal" ferroelectric character, while the tetragonality and grain size increase and the shear piezoelectric coefficients (k15, g15 and d15) improve. For KNN ceramics, the results reveal that the values for remanent polarization as well as for most of the coercive field are quite similar among all compositions. These facts evidenced that Cu2+ may be incorporated into the A and/or B sites of the perovskite structure, having both hardening and softening effects.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe.

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La3+-Mn4+ and Eu3+-Fe3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La3+-Mn4+ and Eu3+-Fe3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications.

Towards Lead-Free Piezoceramics: Facing a Synthesis Challenge.

The search for electroceramic materials with enhanced ferro-pyro-piezoelectric properties and revealing the perovskite type structure has been the objective of a significant number of manuscripts reported in the literature. This has been usually carried out by proposing the synthesis and processing of new compounds and solid solution series. In this work, several methods to obtain ferro-pyro-piezoelectric families of materials featuring the well-known ABO3 perovskite structure (or related) such as BaTiO3, Ba1-xCaxTi1-yZryO3, (Bi0.5Na0.5)TiO3, (K0.5Na0.5)NbO3 and their solid solutions with different cations either in the A or B positions, are presented. For this kind of materials, the challenge for obtaining a single phase compound with a specific grain size and morphology and, most importantly, with the adequate stoichiometry, will also be discussed. The results reviewed herein will be discussed in terms of the tendency of working with softer conditions, i.e., lower temperature and shorter reaction times, also referred to as soft-chemistry.

Nano Coated Lead Free Solders for Sustainable Electronic Waste Management

ABSTRACT Lead has been used in a wide range of applications, but in the past decades it became clear that its high toxicity could cause various problems. Studies indicate that exposure to high concentrations of lead can cause harmful damages to humans. To eliminate the usage of lead in electronic products as an initiative towards electronic waste management (e waste), lead free solders were produced with suitable methods by replacing lead. But lead free solders are not preferred as a substitute of lead because they are poor in their mechanical properties such as tensile strength, shear strength and hardness which are ultimately required for a material to resist failure.Nano-Structured materials and coatings offer the potential for Vital improvements in engineering properties based on improvements in physical and mechanical properties resulting from reducing micro structural features by factors of 100 to 1000 times compared to current engineering materials.