DOCSLIB.ORG

Synthesis of Yttrium Aluminum Garnet Nanoparticles in Confined

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis of Yttrium Aluminum Garnet Nanoparticles in Confined Optical Materials 85 (2018) 275–280 Contents lists available at ScienceDirect Optical Materials journal homepage: www.elsevier.com/locate/optmat Synthesis of yttrium aluminum garnet nanoparticles in confined environment III: Cerium doping effect T Francesco Armettaa, Dariusz Hreniakb, Łukasz Marciniakb, Eugenio Caponettia, ∗ Maria Luisa Saladinoa, a Dipartimento Scienze e Tecnologie Biologiche, Chimiche e Farmaceutiche - STEBICEF and INSTM UdR - Palermo, Università di Palermo, Viale delle Scienze Bld.17, Palermo I, 90128, Italy b Department of Spectroscopy of Excited States, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, ul Okólna 2, Wrocław, Poland ARTICLE INFO ABSTRACT Keywords: Cerium yttrium aluminum garnet (Ce:YAG, CexY3-xAl5O12) nanoparticles doped with different cerium amount were Ce:YAG nanoparticles obtained by calcining the precursors synthesized via co-precipitation in w/o microemulsion for 1 h at 900 °C. The Yttria structural and morphological properties were investigated by using X-ray Diffraction (XRD), Infrared Ce(III) Spectroscopy (IR) and Transmission Electron Microscopy (TEM) coupled with Energy Dispersive X-ray Confined environment Spectroscopy (EDS) in order to investigate the effect of doping level on formation and microstructure of obtained w/o microemulsion nanoparticles. It was found that the composition of the final products strongly depends on the concentration of Phase composition cerium. The formation of single YAG phase was observed only at 0.5% cerium. For other concentrations, a mixture of YAG and yttria phases was obtained indicating an effect of the cerium on stabilization of sesquioxide phase. Optical properties of the single phase powder were also investigated in details. 1. Introduction mechanism of YAG nanoparticles was discussed on the basis of observed particle microstructure and morphology after several thermal treat- For decades, the synthesis of nanoparticles in confined environ- ments [8]. The results indicated that the YAG growth process could be ments such as microemulsions or liquid crystals have been considered influenced by a not complete oxidation of the surfactant (Cetyl- one of the best way to tailor the particle size and shape [1–3]. In trimethylammonium bromide, CTAB). Moreover, it cannot be excluded general, the particle size is influenced by the water/surfactant molar the formation of a complex between aluminum ions and the degrada- ratio [4], by the water/oil molar ratio and by the temperature, which tion products of surfactant, which could affect the availability of alu- affect the microstructure environment in the phase diagram [5]. If the minum to participate in the crystallization process. crystalline phase of the required material is obtained at high tem- YAG, whose cubic structure is in the space group Ia-3d, doped with perature, the precursors prepared in microemulsions can be thermally lanthanides ions, is an important material with interesting technolo- treated. Experimental data demonstrated that the systems maintain a gical applications in displays, X-ray scintillators, lasers, and white light memory of the microstructure used as nanoreactor influencing the final LED which are nowadays well consolidated [9–13]. Notwithstanding, features of the material [6]. the interest of researcher is still growing because the optical properties This kind of studies has been performed to obtain YAG (yttrium of nanocrystals are expected to be dependent not only on the kind of aluminum garnet, Y3Al5O12) nanoparticles via co-precipitation of hy- dopant but also on the synthesis route that may influence particle size, droxides in a bicontinuos microemulsions [7,8]. The preparation in its distribution and morphology [14–17]. In this work, the effect of the microemulsion allowed to obtain nanoparticles with well-defined cerium amount on structure of YAG nanoparticles prepared in micro- shape, not agglomerated and of smaller size (10–45 nm) respect to emulsion has been investigated. those obtained by using other synthetic procedures. Furthermore, the The samples have been prepared in the bicontinuous microemulsion effect of the thermal treatment on the evolution of precursors toward constituted by water/CTAB/1-butanol/n-heptane and calcining the the formation of YAG phase has been also investigated demonstrating precursors at high temperature. The crystalline habit of the obtained the role of the surfactant in the growth mechanism. The possible growth materials has been investigated by using X-ray Diffraction (XRD) and ∗ Corresponding author. E-mail address: [email protected] (M.L. Saladino). https://doi.org/10.1016/j.optmat.2018.08.060 Received 17 July 2018; Received in revised form 21 August 2018; Accepted 23 August 2018 0925-3467/ © 2018 Elsevier B.V. All rights reserved. F. Armetta et al. Optical Materials 85 (2018) 275–280 Infrared Spectroscopy (IR). The morphology and particles size as well as the elemental composition have been investigated by using Transmission Electron Microscopy (TEM) coupled with an Energy Dispersive X-ray Spectroscopy (EDS). Emission and Excitation spectra, lifetimes and quantum efficiency measurements of the single phase powder have been also carried out. 2. Materials and methods 2.1. Materials Cetyltrimethylammonium bromide (CTAB, Aldrich ≥98%), 1-bu- tanol (Aldrich, 99.8%), n-heptane (Sigma-Aldrich, 99%), Y(NO3)3·6H2O (Sigma-Aldrich, 99.8%), Al(NO3)3·9H2O (Sigma-Aldrich, 99.8%), Ce (NO3)3·6H2O (Sigma-Aldrich, 99.99%), ammonia solution (Sigma- Aldrich 28%) and deionized water were used as received. The con- ductance of deionized water was < 1.5 μS/m. 2.2. Preparation of the nanoparticles The precursor synthesis of Ce:YAG nanoparticles at different cerium amount has been performed following the procedure already reported [7,8]. The samples have been prepared in the bicontinuous micro- emulsion R70, resulted the more suitable to obtain separate nano- particles in the previous studies. The yttrium, aluminum, cerium nitrate − solutions (30 - x, 50 and x mmol L 1, respectively) were prepared by dissolving proper amounts of Y(NO3)3·6H2O, Al(NO3)3·6H2O and Ce (NO3)3·6H2O in water in order to obtain 0, 0.1, 0.2, 0.5, 1.0 and 2.0% of cerium atoms with respect to total yttrium plus cerium atoms, ac- cording to the formula CexY3-xAl5O12. For each batch, a white hue sol was instantaneously observed as a Fig. 1. XRD patterns of the obtained powders. * YAG phase peaks, ° Y O phase result of mixing with ammonia microemulsion. A complete precipita- 2 3 peaks. tion occurred in 12 h. The precipitates were thus filtered and repeatedly washed with water to remove residual ammonia, nitrate ions, and surfactant molecules. The obtained white precipitates were over-night emission 300 mm focal length monochromators were in Czerny Turner fi dried at 100 °C, then treated at 900 °C for 1 h. After calcination, solid con guration. Excitation arm was supplied with holographic grating of pellets were formed. The obtained pellets had a yellowish coloration 1800 lines/mm, blazed at 250 nm, while the emission spectra was with tonality influenced by the cerium amount. supplied with ruled grating, 1800 lines/mm blazed at 500 nm. The spectral resolution was 0.1 nm. The R928P side window photo- 2.3. Characterization techniques multiplier tube from Hamamatsu was used as a detector. Quantum efficiency of luminescence was measured using the same XRD patterns were acquired by a Philips PW 1050/39 diffractometer equipment supplied with 30 cm in diameter integrating sphere. in the Bragg-Brentano geometry using Ni-filtered Cu Kα radiation The lifetimes measurements were carried on a femtosecond laser setup (λ = 1.54056 Å) in the 2θ range 5–90° with a step of 0.05° and a time composed of a Coherent Libra-S all-in-one ultrafast oscillator and re- fi for step of 5 s. The X-ray generator worked at power of 40 kV and generative ampli er laser system, with pulse duration less than 100 fs at 30 mA, and the resolution of the instrument (divergent and antiscatter 1 kHz repetition rate, a Coherent OPerA-Solo optical parametric am- plifier and a Hamamatsu C5677 streak camera with time resolution of slits of 0.5°) was determined using R-SiO2 and R-Al2O3 standards free from the effect of reduced crystallite size and lattice defects. The phase 14 ps. ® identification has been performed by using the X'pert HighScore Software. 3. Results and discussion − The ATR spectra were recorded in the 40-4000 cm 1 range, with a − step of 2 cm 1, by using a Bruker Vertex 70 Advanced Research FT-IR Structural and morphological investigation. The XRD patterns of the Spectrometer equipped with Platinum ATR. The measurements have obtained powders are reported in Fig. 1. been performed at 2 hPa. Data have been corrected with a scattering- The undoped powder is constituted by single garnet phase [7,8]. The type baseline. XRD patterns of the samples doped with 0.1 and 0.2% of cerium can be Transmission Electron Microscopy (TEM) micrographs were acquired described in terms of two crystalline phases, the garnet phase and the by using a JEM-2100 (JEOL, Japan) operating at 200 kV accelerating cubic yttrium oxide (Y2O3, yttria) phase, plus a small amorphous voltage, equipped with an energy dispersive X-ray spectrometer (EDS, component probably constituted by aluminum oxide, usually re- Oxford, UK) suitable for element identification. Each powder was presented by a typical diffuse profile centred at about 30° [18], evi- homogeneously dispersed in isopropanol by sonication. A small drop denced in this case by an increased background, (see Fig. S1 of the was deposited on a lacey-carbon grid of 300 mesh, and after complete Support Information, S.I). Reflections corresponding to the garnet solvent evaporation the nickel-copper grid was introduced into the TEM phase are dominant and evident peaks broadening indicates that crys- chamber analysis. tallites are nanometric sizes. Emission and excitation spectra of the nanoparticles were measured On the contrary, the powders doped with higher cerium amount are using the FLS980 Fluorescence Spectrometer from Edinburgh completely crystalline.
Load more

Recommended publications
  • Promotion Effects and Mechanism of Alkali Metals and Alkaline Earth
    Subscriber access provided by RES CENTER OF ECO ENVIR SCI Article Promotion Effects and Mechanism of Alkali Metals and Alkaline Earth Metals on Cobalt#Cerium Composite Oxide Catalysts for N2O Decomposition Li Xue, Hong He, Chang Liu, Changbin Zhang, and Bo Zhang Environ. Sci. Technol., 2009, 43 (3), 890-895 • DOI: 10.1021/es801867y • Publication Date (Web): 05 January 2009 Downloaded from http://pubs.acs.org on January 31, 2009 More About This Article Additional resources and features associated with this article are available within the HTML version: • Supporting Information • Access to high resolution figures • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Environmental Science & Technology is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Environ. Sci. Technol. 2009, 43, 890–895 Promotion Effects and Mechanism such as Fe-ZSM-5 are more active in the selective catalytic reduction (SCR) of N2O by hydrocarbons than in the - ° of Alkali Metals and Alkaline Earth decomposition of N2O in a temperature range of 300 400 C (3). In recent years, it has been found that various mixed Metals on Cobalt-Cerium oxide catalysts, such as calcined hydrotalcite and spinel oxide, showed relatively high activities. Composite Oxide Catalysts for N2O One of the most active oxide catalysts is a mixed oxide containing cobalt spinel. Calcined hydrotalcites containing Decomposition cobalt, such as Co-Al-HT (9-12) and Co-Rh-Al-HT (9, 11), have been reported to be very efficient for the decomposition 2+ LI XUE, HONG HE,* CHANG LIU, of N2O.
    [Show full text]
  • Indium, Caesium Or Cerium Compounds for Treatment of Cerebral Disorders
    Europaisches Patentamt 298 644 J European Patent Office Oy Publication number: 0 A3 Office europeen des brevets EUROPEAN PATENT APPLICATION © Application number: 88305895.0 © intci.s A61K 31/20, A61K 31/28, A61K 33/24 @ Date of filing: 29.06.88 © Priority: 07.07.87 GB 8715914 © Applicant: EFAMOL HOLDINGS PLC Efamol House Woodbridge Meadows © Date of publication of application: Guildford Surrey GU1 1BA(GB) 11.01.89 Bulletin 89/02 @ Inventor: Horrobin, David Frederick © Designated Contracting States: c/o Efamol House Woodbridge Meadows AT BE CH DE ES FR GB GR IT LI LU NL SE Guildford Surrey GU1 1BA(GB) Inventor: Corrigan, Frank ® Date of deferred publication of the search report: c/o Argyll & Bute Hospital 14.11.90 Bulletin 90/46 Lochgilphead, Argyll PA3T 8ED Scotland(GB) © Representative: Caro, William Egerton et al J. MILLER & CO. Lincoln House 296-302 High Holborn London WC1V 7 JH(GB) © Indium, caesium or cerium compounds for treatment of cerebral disorders. © A method of treatment of schizophrenia or other chronic cerebral disorder in which cerebral atrophy is shown, is characterised in that one or more as- similable or pharmaceutically acceptable indium caesium or cerium compounds is associated with a pharmaceutically acceptable diluent or carrier. CO < CD 00 O> Xerox Copy Centre PARTIAL EUROPEAN SEARCH REPORT Application number European Patent J which under Rule 45 of the European Patent Convention Office shall be considered, for the purposes of subsequent EP 88 30 5895 proceedings, as the European search report DOCUMENTS CONSIDERED TO BE RELEVANT Citation of document with indication, where appropriate, Relevant CLASSIFICATION OF THE ategory of relevant passages to claim APPLICATION (Int.
    [Show full text]
  • Atomic Weights of the Elements 1995
    Atomic Weights of the Elements 1995 Cite as: Journal of Physical and Chemical Reference Data 26, 1239 (1997); https:// doi.org/10.1063/1.556001 Submitted: 02 May 1997 . Published Online: 15 October 2009 T. B. Coplen ARTICLES YOU MAY BE INTERESTED IN Atomic Weights of the Elements 1999 Journal of Physical and Chemical Reference Data 30, 701 (2001); https:// doi.org/10.1063/1.1395055 Journal of Physical and Chemical Reference Data 26, 1239 (1997); https://doi.org/10.1063/1.556001 26, 1239 © 1997 American Institute of Physics and American Chemical Society. Atomic Weights of the Elements 1995a) T. B. Coplen U. S. Geological Survey, Reston, Virginia 20192 Received May 2, 1997; revised manuscript received June 13, 1997 The biennial review of atomic weight, Ar~E!, determinations and other cognate data has resulted in changes for the standard atomic weight of 21 elements. The five most significant changes are: boron from 10.81160.005 to 10.81160.007; carbon from 12.01160.001 to 12.010760.0008; arsenic from 74.9215960.00002 to 74.9216060.00002; cerium from 140.11560.004 to 140.11660.001; and platinum 195.0860.03 to 195.07860.002. An annotation for potassium has been changed in the Table of Standard Atomic Weights. To eliminate possible confusion in the reporting of relative lithium isotope-ratio data, the Commission recommends that such data be ex- pressed using 7Li/6Li ratios and that reporting using 6Li/7Li ratios be discontinued. Be- cause relative isotope-ratio data for sulfur are commonly being expressed on noncorre- sponding scales, the Commission recommends that such isotopic data be expressed relative to VCDT ~Vienna Can˜on Diablo Troilite! on a scale such that 34S/32S of IAEA- S-1 silver sulfide is 0.9997 times that of VCDT.
    [Show full text]
  • CHAPTER 8: Diffusion
    1 Chapter 8 CHAPTER 8: Diffusion Diffusion and ion implantation are the two key processes to introduce a controlled amount of dopants into semiconductors and to alter the conductivity type. Figure 8.1 compares these two techniques and the resulting dopant profiles. In the diffusion process, the dopant atoms are introduced from the gas phase of by using doped-oxide sources. The doping concentration decreases monotonically from the surface, and the in-depth distribution of the dopant is determined mainly by the temperature and diffusion time. Figure 8.1b reveals the ion implantation process, which will be discussed in Chapter 9. Generally speaking, diffusion and ion implantation complement each other. For instance, diffusion is used to form a deep junction, such as an n-tub in a CMOS device, while ion implantation is utilized to form a shallow junction, like a source / drain junction of a MOSFET. Boron is the most common p-type impurity in silicon, whereas arsenic and phosphorus are used extensively as n-type dopants. These three elements are highly soluble in silicon with solubilities exceeding 5 x 1020 atoms / cm3 in the diffusion temperature range (between 800oC and 1200oC). These dopants can be introduced via several means, including solid sources (BN for B, As2O3 for As, and P2O5 for P), liquid sources (BBr3, AsCl3, and POCl3), and gaseous sources (B2H6, AsH3, and PH3). Usually, the gaseous source is transported to the semiconductor surface by an inert gas (e.g. N2) and is then reduced at the surface. 2 Chapter 8 Figure 8.1: Comparison of (a) diffusion and (b) ion implantation for the selective introduction of dopants into a semiconductor substrate.
    [Show full text]
  • Contactless, Nondestructive Determination of Dopant Profiles Of
    www.nature.com/scientificreports OPEN Contactless, nondestructive determination of dopant profles of localized boron-difused regions in Received: 11 November 2018 Accepted: 9 July 2019 silicon wafers at room temperature Published: xx xx xxxx Hieu T. Nguyen , Zhuofeng Li, Young-Joon Han , Rabin Basnet, Mike Tebyetekerwa , Thien N. Truong , Huiting Wu, Di Yan & Daniel Macdonald We develop a photoluminescence-based technique to determine dopant profles of localized boron- difused regions in silicon wafers and solar cell precursors employing two excitation wavelengths. The technique utilizes a strong dependence of room-temperature photoluminescence spectra on dopant profles of difused layers, courtesy of bandgap narrowing efects in heavily-doped silicon, and diferent penetration depths of the two excitation wavelengths in silicon. It is fast, contactless, and nondestructive. The measurements are performed at room temperature with micron-scale spatial resolution. We apply the technique to reconstruct dopant profles of a large-area (1 cm × 1 cm) boron-difused sample and heavily-doped regions (30 μm in diameter) of passivated-emitter rear localized-difused solar cell precursors. The reconstructed profles are confrmed with the well- established electrochemical capacitance voltage technique. The developed technique could be useful for determining boron dopant profles in small doped features employed in both photovoltaic and microelectronic applications. An attractive approach for improving light-to-electricity power conversion efciencies of crystalline silicon (c-Si) solar cells is to minimize surface areas of heavily-doped layers. Tis is due to the high recombination-active nature of the heavily-doped layers, causing a signifcant loss of photo-induced electrons and holes. Several solar cell designs employing this concept have been proved to achieve efciencies over 24% such as interdigitated back-contact (IBC)1–3 and passivated-emitter rear localized-difused (PERL)4–6 cell structures.
    [Show full text]
  • Uptake of Nanoparticles of Cerium Oxide and Yttrium Oxide by Acanthamoeba Castellanii (Protozoa) and Daphnia Magna (Crustacea) James R
    Virginia Journal of Science Volume 62, 1 & 2 Spring 2011 Uptake of Nanoparticles of Cerium Oxide and Yttrium Oxide by Acanthamoeba castellanii (Protozoa) and Daphnia magna (Crustacea) James R. Palmieri1, Geneva Gehring, Catherine Minichino, and Shaadi F. Elswaifi Department of Microbiology, Infectious, and Emerging Diseases, Edward Via College of Osteopathic Medicine, 2265 Kraft Drive, Blacksburg, Virginia, USA 24060 ABSTRACT Currently, nanoparticles are synthesized and used at an unprecedented rate for industrial, medical, and research applications. The use of cerium oxide nanoparticles (CeONP) and yttrium oxide nanoparticles (YtONP) results in their spread as contaminants into the environment. Once in the environment, CeONP and YtONP can be taken up by organisms in the food chain where they may pose a public health risk. In this study we determine whether Acanthamoeba castellanii and Daphnia magna uptake CeONP or YtONP from their environment and thereby play a role in the transmission of the nanoparticles. Using electron microscopy, organisms exposed to the nanoparticles were examined. Our results indicate that the nanoparticles are associated with cell and organelle membranes. These findings have implications for the health risks associated with environmental contamination by CeONP and YtONP. INTRODUCTION In this study we determine whether protists and crustaceans play a role in the transfer of cerium oxide nanoparticles (CeONP) and yttrium oxide nanoparticles (YtONP) from the environment to other organisms within the aquatic food chain. Acanthamoeba castellanii, a common protist, and Daphnia magna, a planktonic crustacean, are important components in many aquatic ecosystems. Because acanthamoebae, such as A. castellanni, are aggressive feeders they consume inorganic and organic compounds from their environment, thereby serving as a link by transferring normally unavailable inorganic components to the food chain (Weekers et al.
    [Show full text]
  • Corrosion Protection Mechanisms of Rare-Earth Compounds Based on Cerium and Praseodymium (WP-1618) Objective
    Corrosion Protection Mechanisms of Rare-Earth Compounds Based on Cerium and Praseodymium (WP-1618) Objective Hexavalent chromium containing coatings are widely used to protect U.S. military weapons systems from corrosion, yet present acute health and environmental hazards. This project focused on determining corrosion protection mechanisms for coatings that utilize rare-earth (RE) compounds instead of hexavalent chromium. Understanding the mechanisms by which RE compounds inhibit corrosion would reduce the risk of implementing environmentally friendly coating systems as chromate replacements. Technical Approach Two specific coating systems were examined; cerium-based conversion coatings (CeCCs) and epoxy polyamide primers containing praseodymium-based inhibitors. Prior to the start of the project, both coating systems had demonstrated corrosion protection that could meet current U.S. military requirements for aircraft. The approach taken in this project assumed that RE compounds are not inherently protective. Instead, the appropriate phase of a RE compound has to be incorporated into the proper type of coating to provide corrosion protection in specific environments. As part of the project, mechanistic models for corrosion protection were devised by fully characterizing the phases that were present in as-deposited coatings, the transport processes that occurred during corrosive attack, and the species that formed to passivate the substrates. Results Discovery of sub-surface crevices in substrates with CeCCs led to a significant change
    [Show full text]
  • Interactions of Lanthanides and Liquid Alkali Metals for “Liquid-Like” Lanthanide Transport in U-Zr Fuel
    Interactions of Lanthanides and Liquid Alkali Metals for “Liquid-Like” Lanthanide Transport in U-Zr Fuel THESIS Presented in Partial Fulfillment of the Requirements for the Degree Master of Science in the Graduate School of The Ohio State University By Jeremy Payton Isler Graduate Program in Nuclear Engineering The Ohio State University 2017 Master's Examination Committee: Dr. Jinsuo Zhang, Advisor Dr. Marat Khafizov, Co-Advisor Copyrighted by Jeremy Payton Isler 2017 Abstract One of the major limitations in achieving increased burnup in metallic U-Zr nuclear fuel is Fuel-Cladding Chemical Interaction (FCCI). The migration of the fission product lanthanides from within the fuel to the peripheral is one of the major contributors to FCCI. A “liquid-like” transport mechanism proposes the lanthanide transport is aided by liquid cesium and liquid sodium in the pores of the fuel and at the fuel peripheral. The purpose of this thesis was to provide additional experimental evidence towards this proposed mechanism. This thesis investigated the interaction between the lanthanides and cesium and sodium, with a focus on the solubility of the lanthanides in these liquid alkali metals. First, a prediction of the solubility was calculated using the Miedema model. This prediction was then compared to the inversion crucible solubility experiment performed in this thesis. The solubility experiment studied the temperature and liquid-composition dependence of the lanthanides in liquid sodium, cesium and sodium-cesium mixtures. In addition, the solubility in mixtures shows the various alkali metals concentration effect on the solubility. With the results of differential scanning calorimetry (DSC) experiments, updated phase diagrams for sodium-neodymium and cesium-neodymium were obtained from the experimental data in this thesis.
    [Show full text]
  • Roles of Lanthanum and Cerium in Grain Refinement of Steels During
    metals Review Roles of Lanthanum and Cerium in Grain Refinement of Steels during Solidification Yunping Ji 1,2, Ming-Xing Zhang 3 and Huiping Ren 1,2,* 1 School of Material and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, China; [email protected] 2 School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China 3 School of Mechanical and Mining Engineering, The University of Queensland, Brisbane, QLD 4072, Australia; [email protected] * Correspondence: [email protected]; Tel.: +86-472-595-2289; Fax: +86-472-595-4368 Received: 15 October 2018; Accepted: 25 October 2018; Published: 30 October 2018 Abstract: Refinement of as-cast structures is one of the most effective approaches to improve mechanical properties, formability, and surface quality of steel castings and ingots. In the past few decades, addition of rare earths (REs), lanthanum and cerium in particular, has been considered as a practical and effective method to refine the as-cast steels. However, previous reports contained inconsistent, sometime even contradictory, results. This review summaries the major published results on investigation of the roles of lanthanum or/and cerium in various steels, provides reviews on the similarity and difference of previous studies, and clarifies the inconsistent results. The proposed mechanisms of grain refinement by the addition of lanthanum or/and cerium are also reviewed. It is concluded that the grain refinement of steels by RE additions is attributed to either heterogeneous nucleation on the in-situ formed RE inclusions, a solute effect, or the combined effect of both. The models/theories for evaluation of heterogeneous nucleation potency and for solute effect on grain refinement of cast metals are also briefly summarized.
    [Show full text]
  • Three Related Topics on the Periodic Tables of Elements
    Three related topics on the periodic tables of elements Yoshiteru Maeno*, Kouichi Hagino, and Takehiko Ishiguro Department oｆ physics, Kyoto University, Kyoto 606-8502, Japan * [email protected] (The Foundations of Chemistry: received 30 May 2020; accepted 31 July 2020) Abstaract: A large variety of periodic tables of the chemical elements have been proposed. It was Mendeleev who proposed a periodic table based on the extensive periodic law and predicted a number of unknown elements at that time. The periodic table currently used worldwide is of a long form pioneered by Werner in 1905. As the first topic, we describe the work of Pfeiffer (1920), who refined Werner’s work and rearranged the rare-earth elements in a separate table below the main table for convenience. Today’s widely used periodic table essentially inherits Pfeiffer’s arrangements. Although long-form tables more precisely represent electron orbitals around a nucleus, they lose some of the features of Mendeleev’s short-form table to express similarities of chemical properties of elements when forming compounds. As the second topic, we compare various three-dimensional helical periodic tables that resolve some of the shortcomings of the long-form periodic tables in this respect. In particular, we explain how the 3D periodic table “Elementouch” (Maeno 2001), which combines the s- and p-blocks into one tube, can recover features of Mendeleev’s periodic law. Finally we introduce a topic on the recently proposed nuclear periodic table based on the proton magic numbers (Hagino and Maeno 2020). Here, the nuclear shell structure leads to a new arrangement of the elements with the proton magic-number nuclei treated like noble-gas atoms.
    [Show full text]
  • Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes † § † § † ‡ § † Thibault Cheisson, , Kyle D
    Communication Cite This: J. Am. Chem. Soc. XXXX, XXX, XXX−XXX pubs.acs.org/JACS Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes † § † § † ‡ § † Thibault Cheisson, , Kyle D. Kersey, , Nolwenn Mahieu, , , Alex McSkimming, † † † Michael R. Gau, Patrick J. Carroll, and Eric J. Schelter*, † P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States ‡ Departement́ de Chimie, ENS Paris-Saclay, UniversitéParis-Saclay, 94235 Cachan, France *S Supporting Information generate the anilide complex [Th(NHArF)(TriNOx)] (3)by ABSTRACT: A series of thorium(IV)-imido complexes fl F protonolysis with 3,5-bis(tri uoromethyl)aniline (Ar NH2, was synthesized and characterized. Extensive experimental Scheme 1). and computational comparisons with the isostructural cerium(IV)-imido complexes revealed a notably more Scheme 1. Syntheses of the new Th(IV)-Imido Complexes covalent bonding arrangement for the CeN bond compared with the more ionic ThNbond.The thorium-imido moieties were observed to be 3 orders of magnitude more basic than their cerium congeners. More generally, these results provide unique experimental evidence for the larger covalent character of 4f05d0 Ce(IV) multiple bonds compared to its 5f06d0 Th(IV) actinide congener. hemical bonding in lanthanide and actinide compounds C pushes our understanding and description of metal− ligand interactions. Fundamental understanding of these metal−ligand bonds redefines comprehension of the elements, even 150 years after the disclosure of the periodic trends, and contributes to new applications in reactivity.1 This knowledge from https://pubs.acs.org/doi/10.1021/jacs.9b04061.
    [Show full text]
  • Gain in Polycrystalline Nd-Doped Alumina: Leveraging Length Scales to Create a New Class of High-Energy, Short Pulse, Tunable Laser Materials Elias H
    Penilla et al. Light: Science & Applications (2018) 7:33 Official journal of the CIOMP 2047-7538 DOI 10.1038/s41377-018-0023-z www.nature.com/lsa ARTICLE Open Access Gain in polycrystalline Nd-doped alumina: leveraging length scales to create a new class of high-energy, short pulse, tunable laser materials Elias H. Penilla1,2,LuisF.Devia-Cruz1, Matthew A. Duarte1,2,CoreyL.Hardin1,YasuhiroKodera1,2 and Javier E. Garay1,2 Abstract Traditionally accepted design paradigms dictate that only optically isotropic (cubic) crystal structures with high equilibrium solubilities of optically active ions are suitable for polycrystalline laser gain media. The restriction of symmetry is due to light scattering caused by randomly oriented anisotropic crystals, whereas the solubility problem arises from the need for sufficient active dopants in the media. These criteria limit material choices and exclude materials that have superior thermo-mechanical properties than state-of-the-art laser materials. Alumina (Al2O3)isan ideal example; it has a higher fracture strength and thermal conductivity than today’s gain materials, which could lead to revolutionary laser performance. However, alumina has uniaxial optical proprieties, and the solubility of rare earths (REs) is two-to-three orders of magnitude lower than the dopant concentrations in typical RE-based gain media. We present new strategies to overcome these obstacles and demonstrate gain in a RE-doped alumina (Nd:Al2O3) for the first time. The key insight relies on tailoring the crystallite size to other important length scales—the wavelength of 1234567890():,; 1234567890():,; 1234567890():,; 1234567890():,; light and interatomic dopant distances, which minimize optical losses and allow successful Nd doping.
    [Show full text]