NATIONAL BUREAU OF STANDARDS REPORT

10 872

INTEGRATED SAFEGUARDS EXPERIMENT

Campaign 2 Report

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards' was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation’s science and

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1 Part of the Center for Building Technology.
NATIONAL BUREAU OF STANDARDS REPORT

NBS PROJECT

4314429 August 1972

NBS REPORT

10 872

INTEGRATED SAFEGUARDS EXPERIMENT

Campaign 2 Report

Frederick J. Perella

Charles N. Smith

Approved:

Approved

:

Approved

:

Technical Analysis Division

This report is based on work performed under United States

Atomic Energy Commission Contract Number AT(49 — 2)— 1 165.

IMPORTANT NOTICE NATIONAL BUREAU OF STANDARDS REPORTS are usually preliminary or progress accounting documents intended

for use within the Government. Before material in the reports is formally published it is subjected to additional evaluation and review. For this reason, the publication, reprinting, reproduction, or o p,e n li te ra t u re listing of this Report, either in whole or in part, is not authorized unless permission is obtained in writing from the Office of the Director, National Bureau of Standards, Washington, D.C. 20234. Such permission is not needed, however, by the Government agency for which

the Report has been specifically prepared if tnat agency wishes to reproduce additional copies for its own use. <NBS>

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

CONTENTS

page

Abstract i

Overview 1

I Introduction 7

A. Background and Objectives 7

B. Description of Plant and Process Operations. 9

C. Measurements 9

II Material Balance - Discussion of Inputs 15

A. Feed Material Measurements 15

B. Product Material 18

C. Scrap and Measured Discards 19

III Material Balance Analysis and Results 21

A. Material Measurements 21

B. Material Balance - Results 23

IV Nested Design Experiment 25

A. Background and Objectives. 25

B. Definition of terms used in conjunction with

the nested design experiment 27

C. Description of Method 28

D. Findings 30

E. Summary - Nested Design 34

V Campaign 2 - Summary of Findings 35

VI Conclusions 38

VII Acknowledgements 40

VIII References . 41
FIGURES

page

Figure 1: GE-VNC Plutonium Fuel Laboratory Floor Plan. . 11

Figure 2: Plutonium Fuels Fabrication Line 12

Figure 3: Points and Types of Measurements 14

TABLES

Table 1: Measurement Summary - Campaign 2 13

Table 2: ISE Campaign 2 Plutonia Feed Measurements. . . 17

Table 3: Material Balance . 24
ABSTRACT

The Integrated Safeguards Experiment (ISE) , sponsored

by the USAEC (Division of Nuclear Material Security) was

performed at the General Electric Company, Vallecitos

Nuclear Center, (GE-VNC) Pleasanton, California.

It was a collaborative project with General Electric

Company (GE-VNC) , Brookhaven National Laboratory, Technical

Support Organization (TSO-BNL) and the National Bureau of

Standards, Technical Analysis Division (NBS-TAD) being the

principle participants. Physical measurements were made

and analyzed by GE-VNC. The experimental plan used in the

experiment was the responsibility of TSO-BNL and NBS-TAD.

Experimental support of the non-destructive analysis CNDA)

equipment was provided by TSO and technical and analytical

guidance was provided by NBS and TSO.

The ISE was conducted in two separate campaigns, designated Campaigns 1 and 2. Each Campaign, carried out in a

production environment, involved the fabrication of

mixed oxide PUO

2 -UO 2 fuel rods scheduled for use in a

public utility power plant reactor. The purpose of ISE

was to evaluate the usefulness to Safeguards of a material

balance based on completely measured values for materials

containing plutonium.

1
The material balance for Campaign 1 was calculated and

the result reported in NBS report 10 660 . Also the impact

of the use of non-destructive assay equipment and methods,

which made possible this measured material balance, was

studied and evaluated.

Campaign 2 procedures followed closely those of

Campaign 1, differing only in that certain procedures were

improved as suggested by Campaign 1 experience. These

changes, and their effect on the material balance, are

reported. The significant improvement over the results

obtained for Campaign 1 are noted and reported.

In addition, Campaign 2 included a nested design

experiment which had as its purpose to identify and determine

the magnitude of the several variance components which

contributed to the total measurement error when determining

plutonium content of PuC>2 - UO 2 pellets by the controlled

potential coulometric method (wet chemistry) . Prior to

destructive analysis, these same pellets were measured by

non-destructive gamma and neutron counting methods. A

comparison of results of wet chemistry (destructive)

and non-destructive measurements is reported.

11
Overview

The nuclear materials safeguards program to guard

against the loss or unauthorized diversion of nuclear

materials has long been hampered by the lack of material

balances based entirely on quantitative measurements.

The results of the Technical Studies program in the

development of non-destructive assay instruments have

made possible the timely measurement of many hard-tomeasure materials, leading to the possibility of completely measured material balances.

The Integrated Safeguards Experiment (ISE) was

established at the General Electric (GE) Vallecitos

Nuclear Center (VNC) with the broad purpose of testing

the usefulness, to Safeguards, of materials balance

accounting techniques which employ data based completely

on quantitative measurement. The concept is that, if

all streams and outlets of fissile product are accurately

determined and the uncertainties associated with each

measurement accounted for, then such material balances

would provide control over nuclear materials within a

production facility with a known precision. If such

balances can be made often enough, and if the balances

are precise enough, then to what extent might this satisfy

- 1 -
the requirements of the Domestic Safeguards Program and

specifically for plutonium fuel processing plants?

The ISE was planned to be run in several campaigns,

with changes and refinements in procedures to be added

to each succeeding campaign as suggested by experience in

the previous one. Campaign 1 followed a plan carefully

developed by GE and approved by the AEC and other participating ISE representatives. In addition, the Integrated

Safeguards Experiment team followed details of the work

very closely and thus were able to detect problems with

the procedures, as well as error sources which would

require corrective action to insure more accurate material

balances.* Campaign 2 of the Integrated Safeguards

Experiment was tentatively planned to begin several weeks

after completion of Campaign 1

/ allowing ample time to

analyze Campaign 1 data and to introduce changes in procedures as suggested by the results of Campaign 1 experience.

Since fuel rods fabricated during the ISE were to be

produced for a General Electric Company customer in accordance

with an agreed upon schedule, and since chemical laboratory

latests and analysis for Campaign 1 consumed considerably

more time than anticipated, Campaign 2 processing was

begun before complete results of Campaign 1 were available.

* For detailed discussion and results of Campaign 1,

refer to NBS Report number 10 660, January 1972.

- 2 -
This prevented the preparation of a formal experimental

plan to be submitted to the ISE representatives* for

approval before Campaign 2 was begun.

The proposed experimental plan for Campaign 2 was

therefore informally discussed and items for inclusion ver

bally agreed to. Because of this pre-campaign planning

lacked sufficient depth, resulting in several areas being neglected. For example, insufficient data, primarily in the non-destructive testing area, precluded

a proper evaluation of test procedures, hence there were

no changes introduced in the Campaign 2 NDA of scrap and

waste materials. This was reflected in the results, the

uncertainties associated with Campaign 2 scrap and waste

values being essentially the same and, in some cases, even

larger than those of Campaign 1.

The Campaign 2 plan covered all features of the

Campaign 1 experimental plan and , in addition, included

features which experience in Campaign 1 indicated were

necessary and essential for more accurate material control

These additional features were as follows:

1. Re-organized, more detailed data forms for

recording measurements, calibration data, and material

transfers to and from all areas within the plant.

* AEC , TSO and NBS members assigned to the ISE.

- 3 -
The objective was to reduce to a minimum, errors caused by

incomplete and faulty recording of data, which was an

error source in Campaign 1.

2. A program for multiple measurements including

both NDA and wet chemistry, of plutonium feed. Campaign 1

experience indicated that it was virtually impossible to

produce a meaningful material balance if the plutonium

feed material was not prepared and measured in this manner.

3. A replicate sample - replicate analysis program

for sintered pellets (nested design experiment) . This

was found necessary in order to identify, segregate and

determine the magnitude of the error sources when measuring

Pu content of sintered pellets by several methods.

4. An exhaust filter measurement program.

5. A reorganized, more detailed and more stringent

calibration program. This included more frequent calibration exercises as proposed by ISE representatives.

Campaign 2 involved the processing of approximately

100 kilograms of mixed oxide fuel. The oxide contained

80 percent fissile plutonium and was comprised of two

***• _ enrichments*, 2.58 and 2.38 percent, each consisting of

approximately 50 kilograms.

Since results of Campaign 1 indicated that the major

error sources were due to deficiencies in the measurement

field, special emphasis in Campaign 2 was put on means of

reducing these errors. The multiple measurement program

- Enrichment defined as Pu/( TJ+Pu)

- 4 -
for feed, which involved many individual measurements, resulted in much better agreement between these measurements

than was observed for those in Campaign 1. This was attributed almost entirely to the equilibration treatment which

simply subjected the plutonium dioxide powder to glove box

atmosphere until it adjusted to the relative humidity

of the box before sampling. The agreement between GE-VNC

and New Brunswick Laboratories for wet chemistry assay

values of the same sample material did not, however, show

any appreciable improvement, which suggests a need for

standardization of measurement methods and sampling.

The NDT nested design experiment (replicate sample-replicate

analysis) was accomplished with pointed results. From

information obtained during Campaign 1 it was not discernible whether the observed variation between samples

within a batch was due to variation within a measurement

method or if the batch was actually inhomogeneous. This

experiment characterized the measurement error in gamma

and neutron counting techniques as well as for the controlled

potential coulometric method. Total percent coefficient of

variation of 0.28 reported by G.E. was obtained for the

controlled potential coulometric method for Pu/ (UC>2 + PuC> 2 ) and a small bias was observed between the process and experimental sample results, both measured by the coulometric

method. This bias reflects differences between analysis

periods. Within-pellet variation and between-boat variation

- 5 -
were found to be insignificant. Between-pellet variation

was as large as the dissolution variance. The analytical

v variation was approximately half that of the dissolution

variance. A substantial difference between the total

percent CV for processed pellets vs nested design measurements

may be due to more careful handling during the experiment.

Of the two passive counting methods investigated,

gamma counting with Nal(T) detectors had a smaller uncertainty

than neutron counting, but gamma counting was more sensitive

to the sample configuration.

The material balance, as shown in this report, was

calculated by the NBS representative and care was taken to

include measurements of all streams except those taken on

the absolute filters. These measurements were considered

unreliable and the plutonium content of these filters was

therefore considered as MUF. The material balance calculated for the total Campaign, indicated a MUF of 9.3

grams plutonium with the limit of error of 14.4 grams

Plutonium. LEMUF represents 0.6 percent of throughput

(Pu feed). Since LEMUF for Campaign 1 amounted to 4.0

percent of throughput it is readily seen that the degree of

material control achieved during Campaign 2 was significantly better than that of Campaign 1.

-6-
REPORT ON CAMPAIGN 2 OF THE INTEGRATED SAFEGUARDS EXPERIMENT

I

.

Introduction

A. Background and Objectives

The Integrated Safeguards Experiment (ISE) was conducted at the General Electric Company, Vallecitos Nuclear

Center, (GE-VNC) Pleasanton, California, during the period

August through December 1970. The purpose of the ISE

was to test the usefulness, to Safeguards, of material

balance accounting techniques which employ data based

completely on quantitative measurements. The ISE was

planned to accommodate four major objectives:

1. Evaluate the impact of recently developed nondestructive assay methods on material balance

accounting

.

2. Study methods by which measurement data are

acquired, processed and analyzed in the

facility's nuclear material control system.

3. Evaluate the accuracy and timeliness of currently

employed chemical analysis and sampling.

4. Determine the magnitude of unidentified process

losses for specific unit processes and possible

methods for reduction and isolation of these

losses through use of submaterial balance areas.

A secondary objective was to determine the possibility

of utilizing the results and experience from an ISE to formu-

- 7 -
late numerical criteria and standard procedures for an

"across the board" use in AEC licensee plants.

The main effort to gain these objectives was applied

during Campaign 1 of this experiment. The broad objectives

set forth for the ISE were essentially gained during

Campaign 1. Findings and conclusions on those

objectives were reported in NBS report 10 660 . This

report also points out that objective No. 4, "to determine

the magnitude of unidentified process losses for specific

unit processes and possible methods of reducing them" was

not realized due to the high uncertainties in the PuC>2 feed

measurements thus causing unrealistic LEMUF values. This

problem was corrected prior to start-up of Campaign 2.

However, because of limitations in time and funds, the

investigation of unit process losses was dropped from

Campaign 2 procedures. The planning, project description,

detailed procedures and background features of the ISE, as

well as the results of Campaign 1, are reported in NBS

Report 10 660 . Campaign 2 procedures followed closely those of

Campaign 1 and therefore will not be discussed in detail

in this report. The primary objective of Campaign 2

therefore, was to repeat Campaign 1 procedures, incorporating

changes, refinements and other helpful features as suggested

by the results of Campaign 1, and to compare the results

of both campaigns.

- 8 -
B. Description of Plant and Process Operations

The Plutonium Fuel Laboratory is comprised of two

sections as indicated on the floor plan, Figure 1. The

equipment on the right half is primarily for fabrication

of limited quantities of mixed oxide ceramic fuel for

specific test purposes. In this area also are included

facilities for material and property studies and auxiliary fuel fabrication operations. The equipment in the

left half of the laboratory is primarily for fabrication of

test and demonstration fuel for both fast and thermal reactors. It is in this half of the laboratory that the Integrated Safeguards Experiment was conducted. The work was

done exclusively in a self-contained, interconnected glove

box line. Each individual box contains two inlet and two

otulet ports, each being covered with an absolute filter.

In addition, the outlet port absolute filters are preceded

by double thickness prefilters. Material flow and process

operation in individual glove boxes are shown in Figure 2.

C . Measurements

Measurement effort for Campaign 2 was considerably more extensive and more carefully carried out than that of Campaign 1.

These measurements included wet chemistry for both plutonium

and uranium and non-destructive testing, utilizing calorimetry,

neutron counting and gamma counting. A summary of the number

and type of measurements made on each stream is shown in

Table 1. Also, points in the process line, material involved,

- 9 -
and types of measurements made are shown in Figure 3.

It should be noted that chemical assay values for Pu

content of finished rods, sintered recycle material and

clean scrap were assumed to be the same as for the production material.

- 10 -
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Arrows denote main material flow

Plutonium Fuels Fabrication Line

Figure 2

- 12 -
Table 1

Measurement Summary - Campaign 2

Material Stream

Plutonium Dioxide feed

Preproduction Samples

Production Samples

Scrap & Recycle

Discards

Completed Rods

Special Samples

Number of measurement determinations (a)

Chemical

Assay

16

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II. Material Balance - Discussion of Inputs

A. Feed Material Measurements

The plutonium feed (PuC^) was contained in three

sealed cans. This material was assayed, as received, by

the calorimetry and neutron counting methods. Calorimetry

measurements pointed up a large isotopic discrepancy which

was resolved with the vendor before the cans were opened

to the process line. This feature demonstrated the importance

and usefulness of calorimetry in resolving shipper-receiver

differences on undisturbed feed material. The cans were

then opened, contents dispersed in carefully weighed trays,

and then allowed to reach an equilibration weight. This

procedure was necessary since the PuC>2 (as received from the

vendor) which was packaged under conditions of 4 percent

relative humidity, was to be processed in the glove box

line under an atmosphere of 30 to 60 percent relative

humidity. The PuC>2 was considered equilibrated when

the weight became constant. The average weight gain due

to moisture absorption during the equilibration period

was 0.5 percent. The feed was then sampled, reweighed

and again assayed as previously done before being introduced to the process line for fabrication. This program,

designated as the "multiple measurement" program, involved

many individual measurements. A summary of these measurements is shown in Table 2. The twelve values of plutonium

content shown in Table 2 were based on various averages

- 15 -
and combinations of these measurements. Many of these

measurements were replicate determinations on the same

material or measurements on sampled feed cans. As

originally proposed, the multiple measurement program was

to emphasize calorimetry and coulometry measurements of

feed material after this material was equilibrated. Neutron

counting was added to gain additional experience in this

field. Neutron counting results shown on Table 2 agree

favorably with calorimetry and coulommetry results; however, this may be misleading since canned feed material

of known Pu content (as determined by coulometry) was

used as the standard in these measurements. In addition to the above, and at the request of the AEC , feed

samples were sent to the New Brunswick Laboratory for

independent measurements. These results, shown as

items 4, 5 and 6 on Table 2, compare favorably with results of measurements made by GE-VNC.

The value for the plutonium feed, which was used in

the material balance, was obtained from the equilibrated

weight and chemical assay. (Derived from the statistical

average of 16 individual determinations made on 8 samples,

see measurement values 2 and 3 in Table 2.)

- 16 -
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B. Product Material

Product material consisted of two sets of fuel rods,

ten in each set. One set contained solid pellets, the

other annular pellets with plutonium concentration slightly

higher than that of the solid pellets. Samples were taken

form the boats containing sintered pellets for wet chemistry

plutonium content assay. Sampling plan used was specified

in the GE contract, one pellet from each fourth boat.

A total of 31 assays were made, 15 for 2.58% enrichment and 16 for 2.38% enrichment. Since pellets within a given enrichment were made from the same master blend

an average plutonium concentration value was determined

and used in calculating the plutonium content of the

sintered oxide product. The distribution of values from

these measurements was used to calculate the limit of

error associated with the average Pu concentration value

for the specific enrichment. The total percent Limit of

Error* for each enrichment was then determined by combining the Pu concentration LE and the percent weight LE.**

* LE defined as boundaries within which the true value

of the parameter being measured lies with a probability of

95 percent. Measurements error and sampling error are

assumed to be normally distributed.

** See Reference 5.

- 18 -
c. Scrap and Measured Discards

The measured discards (waste) and scrap packages were

neutron coincidence counted. The procedures used were

essentially the same as those followed in Campaign 1.

The counting times were the same, 10 minutes, independent

of whether the material was low level waste or recoverable

scrap. The calibration program for this measurement

consisted of counting the background and standards and

fitting a curve to the corrected standards values and

their associated Pu 240 equivalent values. This curve

(straight line) has an intercept and a slope, each of which

has an error associated with it. Some of the standards

used were the same as were used for calibration during the

measurement of Campaign 1 materials. In addition, three

other standards utilizing 80 percent fissile plutonium

were incorporated into the calibration curves.

As experienced in Campaign 1, the neutron counting

equipment posed problems of instability during the measurement of Campaign 2 waste and scrap. Therefore, several

calibration curves and sets of parameters had to be

developed. Backgrounds differ with the time of day and the

activity, and this can affect the low level waste measurements.

Another uncertainty and potential problem was introduced into

the system by attempting to count scrap packages which

contained greater amounts of plutonium than the standards

that were used to develop the calibration curve. In these

-19-
cases, the calibration curve was linearly extrapolated.

No additional uncertainty was included to cover this

procedure. The LE associated with the scrap and waste

* measurements, therefore, does not include uncertainties

due to the extrapolation procedure.*

* A more detailed explanation of these measurements

is given in Reference 8.

- 20 -
Ill . Material Balance Analysis and Results

A. Material Measurements

1 . Calorimetry

Feed material that was used in the process line for

fabrication of Campaign 2 fuel was measured by replacement

calorimetry. Total plutonium content was determined to be

2429 grams. The limit of error associated with this measurement amounted to 191 grams plutonium or 7.8%. Although

this LE is considered high, it must be noted that only a

negligible portion (.05%) is due to the calorimeter. The

balance is due to the high uncertainties associated with

the isotopic content of the plutonium sample. The effect

of isotopic analytical errors on replacement calorimetry

assay results were determined.

The contributions for specific isotopes are

Abundance Error Propagated

Isotope o,

*o

o,

*o o,

'o Pu 238 0.249 10 2.66

Pu 239 75.65 0.04 0.01

Pu 240 18.48 0.1 0.03

Pu 241 4.50 0.2 0.01

Pu 242 1.13 0.4 0.00

Am 241 0.860 27.2 (a) 5.06

Total systematic error 7.77%

(a) ARHCO Value-used because ARHCO abundance value

for Am 241 was used. All other uncertainty values

*Reported as shown in GE Fourth Quarterly Report on ISE,

GEAP-12114-7

- 21 -
shown are GE-VNC values.

(b) Propagated error contribution = percent heat contribution times the error.

The feed value obtained by the calorimetric measurement

method agrees closely with that obtained by the wet chemistry

method (2429 vs. 2425 grams). The wet chemistry value was

used to calculate the material balance because of its smaller

limit of error.

2. Analytical Chemistry . As noted in the discussion of

feed measurements in this report the analytical chemistry

value for equilibrated feed material was used to characterize

the Feed.

3. Neutron Coincidence Counting . Neutron coincidence

counting was used to measure measured discards, dirty sintered,

dirty green and clean green scrap. NBS limit of error values

include the following systematic errors due to the following:

(1) Conversion ratios from gPu 240 equivalent units to

gPu includes

:

(a) Isotopic abundance uncertainties for Pu 238,

Pu 240 and Pu 242 and

(b) spontaneous fission rate uncertainties for the

same three isotopes.

(2) Percent uncertainty in standards -- this due to

low number of standards from different blends used for

calibration purposes.

- 22 -
B. Material Balance - Results. The material balance.

which includes measurements of all streams with the exception

of the absolute filters, is shown in Table 3. Absolute filter

results were not used since counting procedures were not

dependable

.

- 23 -
Table 3 - Material Balance

Input

Feed by chemical assay 2425.1 ± 5.8 gPu

Output

• Chem Assay Determination 2256.9 ± 7.5 gPu

Product

Clean Sintered Scrap

Sintered Samples

• Non-destructive Determination 158.8 ± 10.8 gPu

Measured Discards

Other Scrap

Dirty Sintered

Dirty Green

Clean Green

• Samples - Green Mixed Oxide 0.1 ± 0.0 gPu

MUF = Input - Output = 9.3 gPu

LEMUF

= ^LE (INPUT) 2

+ LE (OUTPUT) 2

^

= 14.4 gPu

MUF = 0.38 Percent of throughput (gms. Pu Feed)

All above LE values are independent.

Note - The L.E. values associated with quantities which are

related cannot be combined using the simplified error

propagation formula for unrelated quantities. The reason for this is that the covariance terms, which indicate

the degree that quantities are related to each other,

are not zero and therefore contribute to the total LE

See reference 5 for details.

- 24 -
IV. Nested Design Experiment

The analysis made on the results of the following described experiment was performed by the GE staff and the

report herein was an excerpt from the initial GE draft.

Values and findings are reported as offered by GE . and they

apply only to the results of this experiment. It is the NBS

ISE Representative's opinion that if the NDT equipment had

been tailor-made for the samples used, the results and findings would be different.

A. Background and Objectives . The Integrated Safeguards

Experiment has shown the importance of measuring all streams

in a plutonium process line in order to assure a true material

balance. The uncertainties associated with the assay methods

used must also be determined and it is most important that

the magnitude of these uncertainties be known so that the

most appropriate methods may be applied to the problem of

safeguards control.

During the latter part of Campaign 2 this subject was

aired in a meeting between representatives of GE-VNC and the

ISE-technical representatives which resulted in a special

experiment conducted by GE-VNC to evaluate measurement errors

in several Pu assay methods. Information reported herein is

extracted from the results of this experiment. A detailed

report on this experiment will be issued by GE.

- 25 -
As originally planned, a replicate sample- • replicate

analysis program was set up to compare the plutonium content

of single pellets measured by analytical chemistry (controlled

potential coulometry) , passive neutron assay, and replacement

calorimetry.* Before initiation of routine measurements,

tests were conducted on a single pellet to determine the precision of the planned non-destructive assay techniques.

The observed percent limit of error based on ten assay

determinations was 1.9 and 1.8 for gross and coincidence

counts, respectively. Similar data for replacement calorimetry

based on 5 determinations resulted in percent limit of error

of 12.4. While this value is out of proportion to that observed for the other NDT methods, it should be pointed out

that this is not indicative of calorimeter precision. The

calorimeter available to GE for these tests was not designed

to detect the heat generated by a single pellet sample, which

was in the milliwatt range, and therefore the readings were

not dependable. Because of this, the calorimetry NDA was

deleted from the test and passive gamma measurements were substituted for them.

* Also, since little was known about the several variance

components which make up the total Pu concentration uncertainty,

another phase of this experiment was planned to identify, segregate and determine the magnitude of those components

.

- 26 -
B . Definition of terms used in conjunction with the

nested design experiment . Random Measurement Error The component of random error

in a measuring process due to

chance alone. It does not include

systematic errors introduced by

sampling, miscalibration or other

sources .- Random Measuring Order In this test, the measuring sequence for each sample determined

by the order in which numbers were

selected from a random number

table. A different sequence was

used for each measurement technique

Process Pellets Whole pellets selected and analyzed

during the fuel fabrication process

for product certification.

Percent Relative Error The standard deviation of the random measurement error on Pu concentration for a single determination

divided by the mean Pu fraction and

expressed as a percent.

Treatment The method of preparing pellet

samples to achieve physical forms

having varying degrees of homogenei

ty. From most homogeneous to least

these include (1) pulverized, (2) - 27 -
halved, and (3) whole pellets.

Experiment Pellets Pellets selected at the same time

and from the same firing boats as

process pellets but analyzed at a

later date after the special sample treatment required in the

Nested Design.

Of the two passive counting methods investigated, gamma

counting with Nal (Tl) detectors had smaller error than neutron

counting (0.8% versus 1 to 2% relative) , but the gamma counting

-method was very sensitive to the sample configuration.

Within-pellet variation and between-boat variation were

found to be insignificant. Between-pellet variation was as

large as the dissolution variance. The analytical variation

was approximately half that of the dissolution variance.

C. Description of Method . The basic experimental plan

is known as a balanced, staggered nested design. It is a

balanced design because the test is symmetrical with respect

to a repeating pattern of pellet treatments; it is a staggered

design because some lower level replicate measurements were not

made. This was done to reduce the cost of the experiment without sacrificing any of the estimates of the variance components.

It is a nested design because the lower order terms in the

statistical model are combined with successively higher levels

until they account for the total measurement error. In this

test, the five levels (from low to high) were:

- 28 -
• Variability between aliquants of the same sample

solution (called the "aliquanting error" and

include coulometer errors)

• Variability between solutions made from pulverized

samples (called the dissolution error)

• Variability between the analysis of halves of the

same pellet (called pellet inhomogeneity)

• Variability between individual pellets from the

same firing boats (called between-pellet error)

• Variability between means of firing boats (called

between-boat errors)

The test design involved two classes of pellets. The

process class of pellets included the samples normally

analyzed for Pu/(Pu+U) to certify the product. Process

sample pellets were withdrawn from the same boats as the

experimental pellets but were analyzed in the Spring of

1971 at the time the fuel was fabricated. Although the

experimental class of pellets was withdrawn at the same

time as the process pellets, they were subjected to

special treatments and additional testing before being

measured in the fall of 1971.

Three pellet treatments were defined as follows:

1. Whole pellets - significant differences between

pellets would suggest differences within the batch.

- 29 -
2 . Halved pellets - significant differences between

pellet halves from the same pellet would indicate

inhomogeneity within a pellet.

3. Pulverized pellets - pulverization should assure

homogeneous samples.

D . Findings

General . In comparing controlled potential coulometry

to various counting techniques, it is important to note that

the relative error for the chemical method is for the weight

ratio of plutonium to oxide and the relative error for a

non-destructive counting method (NDA) is for the weight

ratio of certain plutonium isotopes to oxide. Thus, the

relative errors are not directly comparable, since the

chemical relative errors do not include the uncertainty in

the factor for converting the weight of the isotopes measured

by NDT to plutonium weight.

The use of suitable isotopic standards would allow

NDT values to be judged for accuracy. In the absence of

suitable standards, the methods studied can be ranked with

respect to precision for determining Pu/(UC>

2

+Pu02 ) by dividing

the methods into three groups of about equal precision.

Most precise: Controlled potential coulometry

Next most Precise: Non-destructive gamma counting

at 0.414 MeV for whole pellets

- 30 -
Non-destructive gamma counting

at 0.208 MeV for whole pellets.

Less precise: Non-destructive gross neutron

counting with any pellet treatment.

Least precise: Non-destructive gamma counting at

0.414 MeV for both halved and

pulverized pellets.

Non-destructive gamma counting for

the sum of the 0.208 and 0.416 MeV

using halved and pulverized pellets.

Non-destructive coincident neutron

counting for any pellet treatment.

Non-destructive gamma counting at

0.208 MeV for halved and pulverized pellets.

As pointed out in Section IV, the calorimetric results were not indicative of the accuracy of the instrument

since it was not designed to measure heat from a single pellet,

the same rational applies to the neutron and gamma counting

measurements used here since the experimental configuration and

procedure (time, counting statistics, etc.) were not compatible

and direct comparison was not realistic.

- 31 -
Non-Destructive Counting Techniques

1. The relative errors for the best counting technique, in

this experiment (the gamma 0.414 MeV measurement), are

larger than for the controlled potential coulometric determination of Pu/ (U0 2 +Pu0

2

) (0.7 versus 0.28).

2. There was a significant difference in the percent relative errors between the measurement techniques for the

various pellet treatments designed to measure fuel homogeneity within a sample. As expected, the neutron measurements were affected least by the pellet treatments

and the gamma measurements were affected the most.

3. For gamma counting methods, the within-pellet relative

error is smaller for whole pellets than for either halved

i or pulverized pellets.

4. For gamma counting, halved and pulverized pellets had

greater variability between pellets than within pellets.

Thus, variability in preparation was a major source of

the measurement error. Since whole pellets showed consistently less variability between pellets than within

pellets, it was concluded pellet preparation is not a

major source of error for whole pellets.

5. For gross and coincident neutron counting, the relative

errors for both within and between pellets do not depend

on the three types of pellet treatments

.

- 32 -
6. The gross neutron counting method has appreciably smaller

relative errors on homogeneous mixed oxide fuel (within,

between and total) than does the neutron coincident counting method.

Analytical Chemistry

1. The Pu/ (U0 2 +Pu0 2

) analysis by controlled potential coulometry

had the smallest relative percent error of any method of

determination (0.28).

2. The relative error in the Pu/Pu+U determination was 2

times the relative error for the Pu/ (U0

2 +Pu0

2

) determinations (0.54 versus 0.28%).

3. The measurement errors are essentially divided between

"aliquanting" and "pellet dissolution." This means that

significant improvements in both aliquanting and sample

preparation must be made in order to improve the overall

analytical measurement capability.

4. Pellet inhomogeneity, as measured by differences between

pellet halves and between pellets in the same boat, was

too small to be measured, in comparison with other sources of

variation within the experiment. This suggests that the fuel

is homogeneous with respect to plutonium enrichment as

measured by the tested controlled coulometric method.

5. A relative measurement error of 0.06% was observed for 9

- 33 -
National Bureau of Standards samples (calibration standards) .

6. A bias of 0.015% relative in the Pu/ (Pu+U) determinations

was observed between process and experimental samples. It

is believed that this difference was due to uncontrolled

changes within the analytical process between the spring

and fall of 1971.

E . Summary - Nested Design

The test consisted of 15 whole pellets which were chemically analyzed by controlled potential coulometry as part of

the fuel fabrication quality control program (process pellets)

,

and 18 pellets which were given special homogenizing treatments (experimental pellets) . The 18 experimental pellets

were first encapsulated and measured in random order by nondestructive gamma and neutron counting methods. These same

pellets were then chemically dissolved and measured by the

controlled potential coulometric method.

Total % CV for the experimental pellets was calculated

to be 0.28%, as determined by the controlled potential coulometric method for Pu/ (U0 2 +Pu0

2

) , and \ bias of 0.015% relative was

observed between the process and experimental sample results.

This bias reflects differences between two analysis periods.

The variance components which contributed to the total

% CV are as follows:

- 34 -
(1) aliquanting error 0.11%

(2) dissolution error 0.18

(3) pellet inhomogeneity error 0.00

(4) between pellet error 0.18

(5) between boat error 0.07

V. Campaign 2 - Summary of Findings

It was stated in the introduction of this report that

the Campaign 2 experimental plan followed closely that of

Campaign 1, differing only in several areas where Campaign 1

experience indicated that refinements or changes should be made.

These changes were mainly in the calibration of equipment

and material handling and treatment areas. The result of the

Campaign 2 material balance (LEMUF=0.6% of throughput) shows

a significant improvement over that of Campaign 1 (4.0% of

throughput) . This accomplishment is primarily attributed to

the inclusion of the equilibration treatment of the PuC>2 feed,

which resulted in more accurate chemical assay data since

samples from the equilibrated powder were truly representative

of the bulk material.

One of the features added to Campaign 2 was provision of

longer blending time in the feed preparation. It was expected

that this treatment would ensure maximum homogeneity of the

blended oxides f and hence a lower percent coefficient of

variation associated with the Pu content. The results of

such treatment were not, however, as expected. Blending time

for two master blends was essentially the same, but the % CV

35 -
varied considerably

,

as indicated below:

Master blend %CV n

MOIOO 0.43 15

MO101 1.13 16

There was no apparent explanation for this behavior and

during the conduct of Campaign 2 it appeared logical to attribute the difference to pellet inhomogeneity or to lack of

complete dissolution before chemical analysis. This matter

was somewhat enlightened by the results of the nested design

experiment conducted after completion of the Campaign. The

experimental pellets used in the nested design experiment

produced a total % CV of .28. This is in contrast to the

total % CV calculated for the process pellets (from the same

lot as the experimental pellets) of .43. A, possible explanation , after observing this substantial difference is

that the smaller analytical and dissolution variances were

the result of more careful and precise handling in the case of

the experimental pellets.

The nested design experiment was successful in that it

revealed an acceptable estimate of the variability inherent

in the controlled potential coulometric method of measurement

of mixed Pu and U oxides. This variance compares favorably

with results of other laboratories when conducting similar

tests. (6,7) It also characterized the various NDA

methods of measuring Pu content of materials in various forms

within the fabrication cycle and therefore will assist nuclear

- 36 -
fuel manufacturers in selecting and utilizing NDA equipment

where it can best be applied.

Effective utilization of calorimetry can be made if accurate data is known on the isotopic content of the material

measured. Calorimeter results compare very favorably with

chemical analysis results. It is important to note, however,

that the calorimeter must be designed to operate effectively

over the anticipated heat: output range.

Campaign 2 has shown that extra care in handling, recording, blending and measuring material in the process

line will improve material control within the plant.

This can be done with little additional cost, and the

net result may be a monetary gain to the manufacturer.

This campaign has shown that much may be accomplished

by non-destructive counting techniques; however, their

accuracy depends heavily upon carefully prepared standards.

In this campaign, standards used in neutron counting techniques

contained plutonium from sources other than that of the product

being measured. This created variances which were reflected

in the results and, if not accounted for in a material balance,

could be a source of error.

- 37 -
VI. Conclusions

At the completion of Campaign 1 there was evidenced

a strong need for tailoring operational procedures which

would standardize methods of sampling, measurement,

calibration, reporting, material balance and limit of

error calculations. This was so reported in NBS Report

No. 10 660. This need is even more strongly evidenced by

the results of Campaign 2. Experience gained during the

Integrated Safeguards Experiment indicates that such action

could be taken without imposing much hardship upon the

manufacturer. Such action is necessary to assure a common

base for material control in all facilities in the nuclear

fuel field. It would also eliminate many variables confronting the government inspector during a periodical

inspection

.

As was experienced in Campaign 1, the application of

non-destructive testing techniques made the closed measured

material balance in Campaign 2 possible. The results

of the nested design experiment indicates that the counting

techniques tested have relative measuring errors in the

range of 1 to 2 percent. These determinations were

made by highly trained engineers at GE , and under carefully

prepared conditions. In a production environment, however , where

working standards may not be carefully prepared and/or where

operating personnel may not be conscious of the intricacies of

- 38 -
these techniques, the range of errors could be much greater.

Even though this type of equipment will be refined, with

improved accuracy and precision as the equipment is tailored for specific tasks, it is unlikely that NDT methods, as

used in the ISE ,will replace analytical chemical determinations for certain applications. It appears certain that

the application of NDA will have increasing use for process

control and the measurement of heterogeneous materials.

When considering the utilization of NDA in the nuclear fuel

fabrication cycle, a judicious choice of equipment, consistent with requirements of accuracy, contribution to the

LE of MUF, cost of test, and type of material to be measured,

must be exercised.

- 39 -
VII . Acknowledgments

The ISE experiment was conducted in a commercial facility in a production environment. Unlike Campaign 1, where

there was much planning and discussions and interference with

production by the ISE technical representatives, Campaign 2,

under the pressure of delivery of product to the customer,

was performed almost exclusively by General Electric Company

people. In particular, GE was responsible for the conduct of

the "Nested Design Experiment."

As was the case with the Campaign 1 report, the data used

for the preparation of the Campaign 2 report was a collaborative

effort by NBS, TSO (Brookhaven) and GE-VNC. Much of the

data shown in the report was taken from the GE Fourth Quarterly Report of the Integrated Safeguards Experiment, GEAP-12114-7

.

Also, the brief account on the nested design experiment

contained in this report was extracted from the GE-VNC draft

report entitled, "Measurement Errors in Several Pu Assay

methods Based on a Balanced Staggered Nested Design." A

final, detailed report on this work will be issued by GE as

GEAP-12283

.

We wish to acknowledge the assistance provided by the

TSO (Brookhaven) Staff. This report reflects a number of

opinions and thoughts of Sylvester C. Suda and William Marcuse,

authors of the paper, "Integrated Safeguards Experiment at a

Plutonium Fuels Laboratory." (See reference 3.)

- 40 -
VIII. References

1. D. C. Wadekamper, D. M. Bishop and L. T. Hagie,

Integrated Safeguards Experiment, Fourth Quarterly

Report No. GEAP-12114-7

2. D. M. Bishop, L. T. Hagie, W. B. Nelson, M. N. Nelson,

D. C. Wadekamper

"Measurement Errors in General Pu Assay Methods Based

on a Balanced Staggered Nested Design."

GEAP-12283 (DRAFT)

3. Sylvester C. Suda, William Marcuse

"Integrated Safeguards Experiment at a Plutonium

Fuels Laboratory." (Prepared for Submission to the

IAEA Panel on Quantitative Data and Results of

Systems Analysis and Integrated Tests at Vienna, Austria,

October , 1971 .

)

4. C. N. Smith, F. J. Perella

"Integrated Safeguards Experiment - Campaign 1 Report",

NBS Report 10 660. January 1972

5. C. N. Smith

"Limit of Error Calculation used in Integrated Safeguards

Experiment" NBS Report 10 491, July 1971

6. F. N. Smith, "Plutonium Dioxide Feed Materials Handling

and Measurement Standards Studies", Fiscal year 1971

Summary Report WADCO HEDL-TME 71-22

7. Rein, Zeiglar and Metz, "LMFBR/FFTF Fuel Development

Analytical Chemistry Program (Phase II)", March 16, 1970,

LA-4407, TID-4500, UC-80 Reactor Technology

8. C. N. Smith, F. J. Perella

"Detailed Analysis of Measurements in the Integrated

Safeguards Experiment," NBS Report 10812

- 41 -
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