: ; . .!. .>,”’- ,. .. ..,...,..-,...” -...::....‘:;.,.,.-. “-Methods.-, of Chemical Analysis for ,. .,-.-,.,-.... ,”:3.... ., .. ,, -,_ ,.-----.- ”-:.—:....,....-=,.. .,—_...>.. -.+.... ..,,. ,.. ‘....’-’.+ -----....-:.-.:+..-...; ., ;.:.,-.. ..-.>..~-“ FBI? ‘“Uranium-Plutonium Oxide AU* . .. .. ,.. .... ..-: .-’:—...<- ‘ :... -. ---- :. ...”..:.-. ..,.-,-:.. ..- ..--.,:...-.-.:.=. ... ,,... ,. .— - ,.” “. “Fuel and ‘Source Materiak ,r-. — ,....’-., . .:- .:. :. = . .. ,. --:-- -— -. .. —. .. .. .... .— . .. ., . .... ..- “.,.. -.. .- - ..s., ,, .. .. ,:-.’ . ...’ .\- . ...’ ,. ,.. -. Not to be tai;en from this rcto~l . ., . .. .. .,. .. ...” ‘.. .. .. -. “.. .W. 4---W--- -.....+. ..+. _.A .,, . .’-> ....4.* .. .~. ..,?-. ..-. ,.:, - ,. - —-.,- ... - . .. .,-. -. .. --, .-. .=. -.. -.-., ..-. ..-. -.. ,i, . ~ ,. ,. -. .._- --, . ,.- ,. -. .,. .-’. ~. ,. UNITED”STATES ‘ ““ ‘ - ‘- ATOMIC ENERGY COMMISSION . CONTRACT W-7405-ENG. 36 . Thi$ report was”prepa~ed as an-”account‘of work spon&~&i ‘b~ the”United States Government. Neither-the Unit~ Stetes nor the United States Atomic’ -.. ,---- .. A--- EnergV (%’m”mission,nor any ‘of”their’ ernplo~ees, nor *Y ‘&f”their contrac: .- . “tors, sutxontractors, ‘&-thei_~ &mpioyeesj”h%-km”any “warranty, e%pieqsor~m. .,. ., piied, or assumes-any iegai ihbility or responsibil@y for th~ accj&cyj ~m-’ “... -. .. pletengss or i&fuiness of any information, apparatus, product% processdis . ..’.. closed, or- rep”resenti=that its ‘use’wouid not in~inge privateiy- owned-rights: . ..—. ...”.+ ---- .- .-.x -------- -.. ...4. ,. ,.. —-; . .-_.: . ... ..... .’ ...- . ... .-. .— . ...- ,-. .. .. .... .. .. ,--- . ,---- -.-. .,. .. ... - .“ . .. ... , ,. .- ,.—, This report expresses the opinions of-the author or authors and does not nec- essarily refiect the opin”ionsor viewi of the Los Alamos ~ientific Laboratory; . .. —,- --- Printed in the United States of America. Available from National Technical information Service U. S. Department of Commerce ; 6285 Port Royal Road . Springfield, Virginia 22151 Price: Printed (%py $3.00; Microfiche $0.95 Written: February 1971 LA-4622 UC-80, REACTOR Distributed: March 1971 TECHNOLOGY TID-4500 LOS ALAMOS SCIENTIFIC LABORATORY of the University of California LOS ALAMOS ● NEW MEXICO Methods of Chemical Analysis for FBR Uranium-Plutonium Oxide Fuel and Source Materials Edited by James E. Rein George M. Matlack Glenn R. Waterbury Robert T. Phelps Charles F. Metz .——— — t This work was sponsored by the Fuels and Materials Branch of the Division of Reactor Development and Technology of the U. S. Atomic Energy Commission. r ACKNOWLEDGMENTS This report represents the efforts of many indi- viduals to whom the editors are deeply indebted. The eupport and guidance given by G. W. Cunningham, Sol Rosen, J. M. Simmons, D. K. Magnus, and N. Haber- man of the Division of Reactor Development and Tech- nolo~, USA EC, has made its preparation possible. The cooperation of WAD20 personnel, particularly H. G. Powers and W. Delvin, has been invaluable. Many of the methods incorporate information provided by per- sonnel of companies that have cooperated in technical evaluation of the methods. These companies include Atomics International, Babcock & Wilcox (Lyncbburg), General Electric (Sunnyvale), NUMEC, United Nuclear, and WADCO. The editors heartily thank the chemists of the Chemical and instrumental Analysis Group of IASL who developed many of the methods and critically eval- uated all the methods that are presented. ii CONTENTS J2fE Abstract 1 Introduction 1 Dissolution of Uranium-Plutonium Oxides by the Sealed-Tube Technique 5 Determination of the Isotopic Distribution of Uranium in Uranium Dioxide by Mass Spectrometry 9 Determination of the Isotopic Distribution of Plutonium in Plutonium Dioxide by Mass Spectrometry Following Ion Exchange Purification 15 Determfnationof the Isotopic Distribution of Uranium and Plutonium in Mixed-Oxide Pellets by Mass Spectrometry Following Sequential Ion Exchange Separation 23 Determination of the Isotopic Distribution of Uranium and Plutonium in Mixed-Oxide Pellets by Mass Spectrometry Following Liquid-Liquid Extraction Separation 33 Determination of Plutonium-238 fsotopic Abundance by Alpha Spectrometry 43 Determination of Uranium or Plutonium by Controlled Potential Coulometry 41 Determination of Iron by Spectrophotometry 55 Determinant ion of Americium by Gamma Counting in Mixed Oxide Fuel Pellets and Plutonium Dioxide 59 Discussion of Methods for Carbon 65 Determination of Carbon by Combustion to Carbon Dioxide and Its Manometric Measurement 67 Determination of Carbon by Combustion to Carbon Dioxide and Its Chromatographic Measurement 73 Determination of Fluoride and Chloride 77 Determination of Nitride Nitrogen by Spectrophotometry 85 Determination of Phosphorus by Spectrophotometry 91 Determination of Sulfur by Spectrophotometry 95 Determination of Tungsten by Spectrophotometry after Extraction into 3,4- Dimercaptotoluene 101 Determination of Metal Impurities by Emission Spectroscopy Using the Carrier-Distillation Technique 105 Determination of Dysprosium, Europium, Gadolinium, and Samarium by Emission Spectroscopy Following an Amfne Extraction 117 iii CONTENTS Determination of Uranium in Plutonium Dioxide by Spectrophotometry Determination of Total Gas in Mixed Oxide Fuel Pellets and Uranium Dioxide Insulator Pellets (Method A) 12‘7 Determination of Total Gas in Mixed Oxide Fuel PeIlets and Uranium Dioxfde Insulator Pellets (Method B) 133 Determination of Water by Thermal Evolution and Measurement with a Moisture Monitor 139 Determination of Total Volatiles in Ceramic Grade Plutonium Dtoxide and Sample preparation of Plutonium Dioxide for Impurity Analysis 145 Discussion of the Oxygen to Metal (0/M) Ratio Determination 14’7 Determination of the Oxygen to Metal Ratio by Thermogravimetry 153 iv a “ METHODS OF CHEMICAL ANALYSIS FOR FBR UIUNIUM-PLUTONIUM OXIDE FUEL AND SOURW MATERf.ALs Edited by James E. Rein, George M. Mat.lack, Glenn R. Waterbury, Robert T. Phelps, and Charles F. Metz ABSTRACT Twenty-four methods are given for tAe chemical specification analysis of FBR uranium-plutonium mixed oxide fuel and uranium dioxide fnsulator pellets, and for the source materials of ceramic grade uranium dioxide and plutonium dioxide used for their manufacture. The methods include dissolution procedures, uranium and plutonium assay, uranium and plutonium isotopic abundances, metal and non-metal impurities, and other specifications relating to total gas, water, and the oxygen-to-metal ratio. INTRODUCTION rials that may be used in the manufacture of FBR mixed oxide fuel. This report provides methods for the chemical The special calibration materials discussed in the analysis of materials that are used @ the manufacture of methods are available only to those laboratories part ici- uranium-plutonium mixed oxide fuel for fast breeder re- pating in the LMFBR/FFT F program. Further informa- actors (FBRs). The work represented in this report was tion concerning these calibration materials is given in sponsored by the AEC Division of Reactor Development Ref. ‘1. and Technology (DRDT) in support of the development of mixed oxide fuels for F BRs. More specifically, it directly supports the analytical chemistry development program for the characterization of mixed oxide fuels [11 RDT Standard E13-1 “Fast Flux Test Facility Ceram- ic Grade Plutonium Dioxide” (October 1970). for the AEC’s LMFBR/1’FT F Project which is under the [21 R~ Standard E 13-2 “Fast Flux Test Facility Ceram- management of the WA DCO Corporation at Richland, ic Grade Uranium Dioxide” (October 1970). - Washington. [31 RIX Standard E 13-6 “Fast Flux Test Facility Table I summarizes the current chemical specifi- Driver Fuel Pin Fuel Pellet” (October 1970). cations for the fuel and source materials of the LMFBR/ [41 RRT Standard E 13-7 “Fast Flux Test Facility Driver Fuel Pin Insulator Pellet” (October 1970). FFTF. [1-4] The methods presented in this report have [51 R DT Standard E 13-3 “Fast Flux Test Facility been applied to materials having these specifications. Uranyl Nit rate Solution” (October 19’70). In general, these methods also apply to the chemical [61 RDT Standard E 13-4 “Fast Flux Test Facility [51 specification analysis of uranyl nitrate solution and Plutonium Nitrate Solution” (October 1970). [6] plutonium nitrate solution, two possible source mate- [7] R~ Standard F2-6 “Qualification of Analytical Chemistry Laboratories for FFTF Fuel Analysis” (July 1970). 1 TABLE I CURRENT CHEMICAL SPECIFICATIONS FOR LMFBR/FIWF FUEL MATERIALS ‘1-4] Maximum Values (Uxdees Otherwise Stated) Ceramic Grade Mixed Oxide Insulator Specification Uranium Dioxide PEE: %:::. [’1 Fuel Pellets Pellets 1. Plutonium Iso- Not applicable Not applicable topic Composi- tion, wt % 239 + 241 88.0* 0.5 88.0 +0.5 241 2.5 2.5 238 0.15 0.15 sum of others 0.35 0.35 except 240 240 balance balance 2. Uranium Iso- Natural; Natural; Natural; topic Composi- 0.71+ 0.05 0.71*0.05 0.71+ 0.05 tion Wt % 235U Wt %. z% Wt % 2=U 3. Total Plutonium Not applicable Minimum 85.0 * 3.5$% of Not applicable Content, at time of nominal Wt% packaging value for individual Minimum 87.5 pellets and after heating * 1.0% of to 9500C nominal value for lot average 4. Total Uranium Minimum 86.6 2000 pg/g * 19 relative None given Content wt % on dry of actuaf basis uranium content 5. Americium, Not applicable 0.25 0.25 Not applicable Wt %,of Plu- tonium 6. Carbon, jfg/g 150 200 150 200 7. Chlorine, ~g/g 25 50 20 20 8. Fluorine, pg/g 25 25 10 10 9.