The document summarizes four presentations on crystal growth and material characterization given at an oral communications afternoon event. The first talk discusses crystal growth techniques like Czochralski and zone melting used to grow fluoride and tungstate crystals for optical applications. The second talk presents photoluminescence and magnetic measurements of Cr3+-doped Cs2NaAlF6 crystals. The third talk reports on luminescence properties of CdSiO3 phosphor produced via sol-gel method and doped with Mn2+ and Gd3+. The fourth talk examines correlation between molecular dynamics, packing structure, and optical properties of phenylene-vinylene/aliphatic multiblock copolymers.
The document summarizes four presentations on crystal growth and material characterization given at an oral communications afternoon event. The first talk discusses crystal growth techniques like Czochralski and zone melting used to grow fluoride and tungstate crystals for optical applications. The second talk presents photoluminescence and magnetic measurements of Cr3+-doped Cs2NaAlF6 crystals. The third talk reports on luminescence properties of CdSiO3 phosphor produced via sol-gel method and doped with Mn2+ and Gd3+. The fourth talk examines correlation between molecular dynamics, packing structure, and optical properties of phenylene-vinylene/aliphatic multiblock copolymers.
The document summarizes four presentations on crystal growth and material characterization given at an oral communications afternoon event. The first talk discusses crystal growth techniques like Czochralski and zone melting used to grow fluoride and tungstate crystals for optical applications. The second talk presents photoluminescence and magnetic measurements of Cr3+-doped Cs2NaAlF6 crystals. The third talk reports on luminescence properties of CdSiO3 phosphor produced via sol-gel method and doped with Mn2+ and Gd3+. The fourth talk examines correlation between molecular dynamics, packing structure, and optical properties of phenylene-vinylene/aliphatic multiblock copolymers.
(16h00 - 17h45) PREPARATION AND OPTICAL CHA- RACTERIZATION OF MATERIALS [15/05/12 - 16h00 - Room 1] Crystal growth: from bulk to microcrystals., S. L. Baldochi, J. R. Moraes, G. H. G. Naka- mura, F. R. Silva, L. R. L. Soares, Instituto de Pesquisas Energeticas e Nucleares - IPEN - CNEN/SP Crystal growth is an amazing activity. It is one - eld usually not directly classied as physics in view of chemistry and materials engineering approaches, howe- ver, for a deep understanding of crystal growth, requi- red to achieve the fabrication of useful crystalline ma- terials, basic principles of physics are needed. Ther- modynamics is essential to understand a phase dia- gram denoting equilibrium states plotted as functions of temperature and concentration, fundamental para- meters on crystal growth. The heat and mass trans- port phenomena also play a signicant role in crystal growth theory and in the control of defects in crys- tals hosts. The knowledge about the arrangement of atoms in solids (crystallography) and the inuence of the crystals geometry is also relevant. The crystal- lographic direction may be a main parameter on the defects propagation or growth rate during the fabrica- tion of a single crystal. In view of multi-phenomena and multi-scale interactions present in crystal growth process, advances in this eld have been driven by a combination of experimental eort (motivated from new devices and applications), characterization process and development of theoretical models. The present work aims to discuss the motivation for, some important early results, and some current works of our laboratory on bulk and micro crystal growth. We review the crystal growth technologies employed (Czochraslki, Zone mel- ting and micro pulling down) and describe progress of our group in the last years in optimizing crystal growth of uorides (BiY F 4 , LiY F 4 , BaY 2 F 8 ) and tungsta- tes (NaLa(WO 4 ) 2 , LiLa(WO 4 ) 2 ) materials aiming the development of optical applications (mainly laser hosts and scintillators). The requirements with respect to size and quality of crystals for dierent applications and with respect to complexity of crystal growth problems are discussed based on thermal, optical and structural characterizations of the obtained samples. [15/05/12 - 16h30 - Room 1] Optical and magnetic properties of the single crystal system Cs 2 NaAlF 6 with Cr 3+ as substitu- tional impurity, Sandra da Silva Pedro, Mario Souza Reis, UFF - RJ - Brazil, Sandra da Silva Pedro, Lilian Pantoja Sosman, UERJ - RJ - Bra- zil, Heloisa Nunes Bordallo, University of Cope- nhagen - Copenhagen - Denmark, European Spallation Source - Lund - Sweden, Ricardo Borges Barthem, UFRJ - RJ - Brazil, Fabiano Yokaichiya, LNLS - SP - Brazil Insulating materials doped with transi- tion metals have been studied in the last years with a great interest by its optical properties and technological applications as, for example, tunable solid state lasers, optical sensors, communications, electronics devices. In these compounds, the electronic transitions inside the incomplete shell leads to a broad absorption and emis- sion bands, with high quantum yield, depending on the dynamics of the crystalline environment to which the impurity ion is inserted. The aim of this work is to pre- sent photoluminescence and excitation spectra at room and low temperatures and some preliminary magnetic measurements of the system Cs 2 NaAlF 6 with several concentrations of Cr 3+ ion as substitutional impurity. The optical spectra were analyzed from Tanabe-Sugano theory. The luminescence spectra at 300 K show a broad band whose intensity depends on the impurity concentration. The band was attributed to the spin- allowed transition 4 T 2 ( 4 F) 4 A 2 ( 4 F) of Cr 3+ ions in octahedral sites. At 5 K the spectra show a very rich structure, with a zero-phonon line, attributed to the 2 E( 2 G) 4 A 2 ( 4 F) spin-forbidden electronic tran- sition with vibrational modes associated to the octahe- dral Cr 3+ ion. The spectra also show that the Cr 3+ ion occupies two non-equivalent sites. In the obtained ex- citation spectra for samples doped with 0.1% and 1.0% of Cr 3+ were observed the spin-allowed electronic tran- sitions 4 A 2 ( 4 F) 4 T 1 ( 4 F), 4 A 2 ( 4 F) 4 T 2 ( 4 F) and 4 A 2 ( 4 F) 2 E( 2 G). With Tanabe-Sugano energy ma- trices for the d 3 conguration, the values of the crystal eld parameter Dq, the Racah parameters B and C were calculated and the position of the energy transiti- ons 4 A 2 ( 4 F) 4 T 1 ( 4 P) and 4 A 2 ( 4 F) 2 T 1 ( 2 G) were estimated. Heat capacity measurements were realized with magnetic elds of 0 T, 5 T and 10 T between 2 and 50 K at the 1.0% and 30.0% samples. The change in specic heat measurements was observed at tempe- ratures below 10 K. This behavior was attributed to the Schottky eect caused by the splitting of the crystal - eld of the dopant ion energy levels. Preliminary analysis indicates the presence of additional magnetic eects at low temperatures with change of magnetic eld. Acknowledgments: FAPERJ and CAPES for nancial support, and Prof. Dr. Fernando Iikawa (IFGW- UNICAMP) by collaboration in the optical measure- ments. [15/05/12 - 16h45 - Room 1] Luminescence mechanisms of the phosphor CdSiO 3 produced via sol-gel route, Carolina Melo de Abreu, Z elia Soares Ma- cedo, UFS - SE - Brasil Cadmium silicate CdSiO 3 is a long lasting phosphorescent material of high technological interest. This material has potential applications in areas such as emergency lights, opto- electronic devices and coating of ceramic tiles for use in radiodiagnostic rooms. It presents intrinsic luminescence with long lasting emission, with light persistence of about 3 h. Traditionally, this phosphor is prepared by a solid state reaction. In this work, CdSiO 3 was produced via a modied sol-gel route. The phosphorescent properties were determined for the material in pure state, doped with Mn 2+ and Gd 3+ , and also co-doped with (Mn 2+ , Gd 3+ ). The starting materials used to produce the gel were cadmium oxide (CdO) and tetraethylorthosilicate (TEOS). During the synthesis, several parameters such as stability conditions, time and temperature of the calcinations 2 Oral Communications Afternoon (16h00 - 17h45) - 15/05/12 were tested to produce single crystalline phase CdSiO 3 . The single crystalline phase CdSiO 3 was obtained after calcination at 1000 o C for 3 h. The optical properties of the synthesized powders were studied via optical absorption (OA), photoluminescence (PL), lifetime measurements and radioluminescence (RL). The opti- cal absorption measurements suggest the presence of the band gap of CdSiO 3 at 5,6 eV (221 nm). These measurements also presents an absorption band at 4,7 eV (263 nm) possibly related to the absorption of self- trapped excitons. The PL and RL emission spectra of the pure, doped and co-doped samples presented broad emission bands near 408 nm, 480 nm and 590 nm with dierent relative intensities. Lifetime measurements presented three decay processes. Combining AO results with PL and RL spectra, three possible luminescent channels were identied: (i) direct recombination of electrons from the conduction band with holes from the valence band ( em = 408 nm); (ii) recombination of excitons ( em = 480 nm); (iii) emission from color centers possibly related to impurities, intrinsic defects and dopants present at low concentration ( em = 590 nm). The luminescence intensities and lifetimes increase signicantly with the presence of dopant. This work enabled the development of phosphors CdSiO 3 with violet (CdSiO 3 undoped), blue (CdSiO 3 :Gd 3+ ) and orange (CdSiO 3 :Mn 2+ ; CdSiO 3 :Mn 2+ , Gd 3+ ) emission. [15/05/12 - 17h00 - Room 1] Correlation between molecular dynamics and packing and optical properties on phenylene- vinylene/aliphatic multiblock copolymers, O.D. Bernardinelli, Instituto de Fsica de Sao Car- los - Universidade de Sao Paulo, S.M. Cassemiro, Paulo Scarpa Polymer Laboratory - Federal University of Parana, L.A.O. Nunes, Instituto de Fsica de Sao Carlos - Universidade de Sao Paulo, T.D.Z. Atvars, Chemistry Institute - State University of Campinas, L. Akcelrud, Paulo Scarpa Polymer Laboratory - Federal University of Parana, E.R. deAzevedo, Instituto de Fsica de Sao Carlos - Universidade de Sao Paulo Optoelectronic devices with polymer lms as active layers have become an important topic in science and technology of todays electronic engineering. Chemical modications to conne the degree of the polymer conjugation to well dened values opens the possibility of engineering materials with tunable gaps to control the color of the devices emission. One way of achieving that is preparing multiblock conjugated/non- conjugated copolymers where the non-conjugated units are aliphatic spacers. This work reports a detailed spectroscopy study of a series of multi block conjugated non conjugated copolymers built by p-phenylene type units (PV) and an octamethylene spacers, namely, poly(1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2- ethenylene) (LaPPS18). The relative proportions of the PV and aliphatic segments were estimated based on Solid-state nuclear magnetic resonance spectroscopy NMR and Raman spectroscopy. The morphology was characterized by Wide Angle X-ray Diraction; 1 H Wi- deline Dipolar Chemical Shift Correlation (DIPSHIFT) and Centerband-Only Detection of EXchange (CO- DEX) NMR data, that together with glass transition temperatures allowed us to identify the groups involved in the molecular dynamics. These dierent structural properties were used to explain the photoluminescence properties in terms of peak position and spectral prole. Putting all data together, we concluded that the higher amount of nano-scale crystalline phase is responsible for both the well resolved vibronic structure of the photoluminescence band and for the higher T g value of the copolymer with greater relative content of PV units. [15/05/12 - 17h15 - Room 1] Inuence of co-dopant in the Eu reduction in the SrAl 2 O 4 host, P. J. R Montes, , Instituto Federal de Sergipe, Felipe M. S. Soares, Claudi- ane dos Santos, M. V. dos S. Rezende, M. E. G. Valerio, Universidade Federal de Sergipe Rare- earth-doped aluminates serve as an important class of phosphor for commercial applications, especially in the areas of safety improvement and energy saving. Stron- tium aluminates (SrAl 2 O 4 :Eu 2+ , Dy 3+ ) and barium aluminates (BaAl 2 O 4 :Eu 2+ , Dy 3+ ) represent a class of materials that may exhibit long lasting phosphorescence and luminescence when doped with trivalent and diva- lent rare-earth ions. Most aluminates are activated by Eu 2+ ions, and to obtain the rare earth with this va- lence the trivalent rare earth oxide is usually used as the starting material. To reduce the rare earth from Eu 3+ - Eu 2+ it is necessary to use particular schemes in the production of the rare earth containing sample. Many such schemes have been used and developed. The most common scheme is to use N 2 -H 2 or H 2 , or CO 2 or CO as reducing agents when the rare earth contai- ning sample is calcined. In this work, the DXAS te- chnique (Dispersive X-ray Absorption Spectroscopy) is used to follow the XANES spectrum of the Eu ions du- ring the calcinations program in H 2 atmospheres in the SrAl 2 O 4 :Eu 2+ , RE 3+ (RE= Ce 3+ , Gd 3+ , Dy 3+ , Er 3+ , Y 3+ ) samples. Analysis of the reduction dynamics can give information of the synthesis process and DXAS technique can be used to follow it. The pre-calcined samples of SrAl 2 O 4 :Eu 2+ , RE 3+ (RE= Ce 3+ , Gd 3+ , Dy 3+ , Er 3+ , Y 3+ ) samples were prepared at 600 o C via a sol-gel proteic route. DXAS spectra were obtained as a function of temperature excited at the LIII edge of Eu ions during the synthesis. DXAS spectra exhi- bit changes of absorption edge position associated to the LIII edge of the Eu ions during heating and coo- ling of samples. The ratio of absorption edge Eu 3+ / Eu 2+ was investigated to verify the eciency of reduc- tion agents in the stability of Eu 2+ ion in the matrix. Eu 2 O 3 was used as reference sample. The results show that the reduction of Eu occur at the calcinations tem- perature (1100 o C), but the process is reversible upon cooling down to room temperature. The results also shows that the ratio of absorption edge Eu 3+ / Eu 2+ chance with dierent co-dopant.(This work was parti- ally supproted by CAPES, CNPq, FINEP and LNLS. MVSR acknowledge the PhD grant from CNPq). [15/05/12 - 17h30 - Room 1] Radioluminescence mechanism of Pr-doped BaY2F8, Adriano Borges Andrade, Ana Ca- rolina Santana de Mello, Marcos Vinicius dos 15/05/12 - Oral Communications Afternoon (16h00 - 17h45) 3 Santos Rezende, M ario Ernesto Giroldo Va- lerio, Universidade Federal de Sergipe - UFS, Sonia Licia Baldochi, Instituto de Pesquisas Energeticas e Nucleares - Centro de Laser e Aplicac oes CLA-IPEN In this work were used the techniques XAFS (X- Ray Absorption Fine struture) and XEOL (X-Ray Ex- cited Optical Luminescence), held in Brazilian Synch- rotron Light laboratory in Campinas-SP, for the study of processes that cause the luminescence of the scin- tillator BaY 2 F 8 :2%Pr 3+ . Important new properties on the mechanism of the luminescent material were ob- served. The spectrum XEOL the of BaY 2 F 8 :2%Pr 3+ showed the typical emissions ion Pr 3+ , with emissions at 482, 525, 555, 607, 642 and 722 nm corresponding to transitions 3 P 2 - 3 H 5 , 3 P 1 + 1 I 6 - 3 H 5 , 3 P 2 - 3 F 4 , 1 D 2 - 3 H 5 , 3 P 2 - 3 F 4 and 1 D 2 - 3 H 5 , respectively. The XEOL emission intensity measured as function of pho- ton energy X-ray at the absorption edges L I , L II and L III to Ba 2+ , and was less intense in edge L III of Pr 3+ because it is a dopant. The XEOL is however very dif- ferent from a characteristic absorption curve measured in the X-ray transmission mode after edges absorption intensity XEOL (already normalized by the intensity of X-ray beam incident) increases monotonically with the excitation energy, revealing that the eciency scintilla- tion is greater the greater the energy of photons. These results suggest a model for the mechanism of scintilla- tion BaY 2 F 8 :2%Pr 3+ when excited by X-ray, due to the charge generating process based on absorption of X-ray photons on the trac of carriers between the bands of conduction/valence and traps and in the process of radi- ative recombination of carriers that transfer light energy for the Pr 3+ . (Work supported by Capes/Fapitec and CNPq)
Electrochemical Sensor Based On Reduced Graphene Oxide/carbon Black/ Chitosan Composite For The Simultaneous Determination of Dopamine and Paracetamol Concentrations in Urine Samples