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The original document from which this microfiche has been prepared has these imperfections: missing pages/iigw1 numbered: wrong pagination poor overall printing quality combinations of the above other INIS Clearinghouse I-A.E.A. P.O. Box 100 A-1400, VIENNA AUSTRIA BARC/1993/P/008 FUEL CHEMISTRY DIVISION ANNUAL PROGRESS REPORT FOR 1990 Edited by S. Vaidyanathan 1993 BARC/1993/P/008 so o o 2 GOVERNMENT OF INDIA £j ATOMIC ENERGY COMMISSION CO FUEL CHEMISTRY DIVISION ANNUAL PROGRESS REPORT FOR 1990 by R. Vaidyanathan FueJ Chemistry Division BHABHA ATOMIC RESEARCH CENTRE BOMBAY, INDIA 1993 BARC/1993/P/OO8 BIBLIOGRAPHY DESCRIPTION SHEET FOR TECHNICAL REPORT <as per IS s 94OO - 1980) 01 Security classication s Unc1ass i f i ed 02 Distribution ; External 03 Report status : New 04 Series : BARC External 05 Report type : Progress Report 06 Report No. : BARC/1993/P/008 07 Part No. or Volume No. : 08 Contract No. : Fuel Chemistry Division Annual Progress Report for 199O 11 Collation : 161 p., 7 figs., 52 tabs. 13 Project No. s 20 Personal author (s) : R. Vaidyanathan <ed.) 21 Affiliation of author (s) : Fuel Chemistry Division, Bhabha Atomic Research Centre, Bombay 22 Corporate author(s) : Bhabha Atomic Research Centre, Bombay-400 085 23 Originating unit : Fuel Chemistry Division, BARC, Bombay 24 Sponsor(s) Name : Department of Atomic Energy Type : Government 30 Date of submission : October 1993 31 Publication/Issue date November 1993 contd. Hi) (ii) 40 Publisher/Distributor : Head, Library and Information Division, Bhabha Atomic Research Centre , Bombay 42 Form of distribution : Hard Copy 5O Language of text : English 51 Language of summary : Eng1ish 52 No. of references : refs. 53 Given data on : 60 Abstract :The progress report gives brief descriptions of the various activities of the Fuel Chemistry Division of Bhabha Atomic Research Centre, Bombay for the year 199O. The descriptions of activities are arranged under the headings: Fuel Development Chemistry, Chemistry of Actinides, Quality Control of Nuclear Fuels, and studies related to Nuclear Materials Accounting. At the end of the report, list of papers published in journals and presented at var ious canferences/symposia is also given. 70 Keywords/Descriptors : RESEARCH PROGRAMS; BARC; PROGRESS REPORT; NUCLEAR FUELS; SOL-SEL PROCESS; ACTINIDESj CHEMICAL PREPARATION; CERAMICS! SUPERCONDUCTORS; URANIUM; PLUTONIUM; SOLVENT EXTRACTION; MICOSPHERES; ION EXCHANGE MATERIALS? CALIBRATION STANDARDS; QUALITY CONTROL; ACCOUNTING; NUCLEAR MATERIALS MANAGEMENT; RADIOMETRIC ANALYSIS 71 Class No. : INIS Subject Category : B161O; B13OO 99 Supplementary elements : The previous progress report was published as BARC/1993/P/0O7 covering the period 1989 PREFACE This document, a report on the activities carried out in Fuel Chemistry Division during the year 1990, has been been divided into four sections. In the £irst section,viz., Fuel Development Chemistry section, work related to sol-gel process development and studies in high temperature kinetics and thermodynamics are being reported upon. While carbothermic conversion of UO2 + OH , carbothermic reduction of uranium oxides, oxidation behaviour of OH microspheres, preparation of superconducting YBa2Cu207-x ceramics are some of the areas of work in sol-gel process development, the topics studied in high temperature kinetics and thermodynamics are concerned with measurement of some of the thermodynamic parameters for materials like LiaCrO*, Li2Mo04, BaZrOs, Cs(Rb)U40i2, Cs(Rb)U40i3 etc., and optimum conditions for preparation of PuF4 and plutonium metal. Work relating to studies on the solid state, solution and process chemistry of actinides are reported in the second section,namely. Chemistry of Actinides. Solid state reactions in Na-Cr-0-0, K-Cr-U-0 systems and X-ray, thermal and infra-red studies on rubidium/caesium uranyl oxalate hydrates, besides studies on superconducting materials are the areas covered in solid state chemistry. In solution chemistry, the work reported refers to solvent extraction studies with Di-2 ethyl hexyl phosphoric acid, ion exchange behaviour of Plutonium from aqueous basic media and ion exchange studies using mixed solvent media. Process Chemistry encompasses solvent extraction studies for the recovery of Plutonium from oxalate effluents, extraction of plutonium from phosphate containing nitric acid solution using DHDECMP (Dihexyl-H,N- diethyl carbomyl methyl phosphate) as an extractant and byproduct actinide recovery from high level waste. Also included is the work carried out for the separation and (ii) purification of uranium and thorium using macroporous cation exchange resins Amberlyst-15 and Tulsion-42. Work reported in the third section called Chemical Quality Control of Nuclear Fuels relates to studies carried out on analytical methods, primary chemical assay standards and analytical services rendered. Electrochemical, titrimetric, mass spectrometric and spectrophotometric studies for the chemical quality control of nuclear materials are reported upon in analytical methods. Studies on the preparation and characterisation of primary chemical assay standards for uraniumm and plutonium viz., K2Pu(S0<)4 and Rb2U(SCU}3 as well as a report on the nature and number of analytical services rendered are also mentioned in this section. In the fourth section. Nuclear Materials Accounting, studies on quality control data on mechanical properties of zircaloy tubes for BWR fuel, autocorrelation among time sequence of MUF values plus the related software development on the NUMAC computer system and an overview of the computer-based database mannagement system for storage and retrieval of information related to nuclear materials accounting received from all the DAE facilities are reported. A list of papers published in Journals and presented at different conferences/symposia during the year and an authors' index have also been included. The Editor expresses his sincere thanks to Dr. D.D.Sood, Director, Radiochemistry & Isotope Group for sparing his valuable time to scan the draft version of this document and for offering his valuable comments and suggestions. He owes his thanks to Sri. Satya Jyothi for his help and cooperation in organising and preparing this report and to Smt. Sudha Radhakrishnan and Smt. Snehal R. Athalye for their faultless typing and sjord-processing of it. (iii) CONTENTS 1. FUEL DEVELOPMENT CHEMISTRY 1 1.1 Sol-Gel Process Development 1 1.2 High Temperature Kinetics and Thermodynamics 20 2. CHEMISTRY OF ACTINIDES 61 2.1 Solid State Chemistry 61 2.2 Solution Chemistry 73 2.3 Process Chemistry S3 3. CHEMICAL QUALITY CONTROL OF NUCLEAR FUELS 105 3.1 Analytical Methods 105 3.2 Primary Chemical Assay Standards 135 3.3 Analytical Services 140 4. NUCLEAR MATERIALS ACCOUNTING 143 4.1 Statistical Studies 143 4.2 NUHAC Database Management System 146 5. Publications during the year 1990 148 6. Authors' Index 156 1. FUEL DEVELOPMENT CHEMISTRY 1.1 Sol -0«l FrooMS Development 1.1.1 Preparation of Carbon Dispersed OOa Gel Particles T.V. Vittal Rao,Y.R. Bamankar, S.K. Mukerjee.V.N. Vaidya and D.D. Sood Work on preparation of UO3 + C gel microspheres by internal gelation technique was continued. During this period, 115 kg of this material was supplied to the Radiometallurgy Division for fabrication of dense (JO2 pellets via sol-gel microsphere pelletization (SGMP) route. For the preparation of this material standardised feed composition of [U] = 1.1 M, [HMTA, Urea]/[U] =1.5 and 30 g of carbon per litre of feed was used. For gelation of droplets an assembly with capacity of 10 kg/day was used. 1.1.2 Gelation Behaviour of Thorium Nitrate Solution with Hexamethylene Tetramine (HMTA) and Urea N. Kumar, V.R. Ganatra, R.K. Shanna, S.K. Mukerjee, V.N. Vaidya and D.D. Sood In continuation of the work on the preparation of TI1O2 microspheres by internal gelation process, following experiments were carried out to get a better understanding of the gelation process. Gelation of thorium nitrate solution was studied as a function of [Th], [HMTA], [Urea]/[Th] and temperature. Product gel was classified into three main categories, namely, soft opaque gel, hard opaque gel and transparent gel. Out of these, only hard opaque gel is of interest to obtain defect free TI1O2 microspheres.