Designation: C1817 − 16

Standard Test Method for

The Determination of the Oxygen to Metal (O/M) Ratio in
Sintered Mixed Oxide ((U, Pu)O2) Pellets by Gravimetry1
This standard is issued under the fixed designation C1817; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope C833 Specification for Sintered (Uranium-Plutonium) Diox-

1.1 This practice is an alternative method to Test Method ide Pellets
C698 for the determination of the oxygen-to-metal atom ratio C859 Terminology Relating to Nuclear Materials
(O/M) in sintered mixed oxide fuel (MOX) pellets. The method C1068 Guide for Qualification of Measurement Methods by
presented in Test Method C698 is a one-step thermogravimet- a Laboratory Within the Nuclear Industry
ric method for determining O/M ratio in sintered MOX C1672 Test Method for Determination of Uranium or Pluto-
powders and pellets. As stated in Test Method C698, thermo- nium Isotopic Composition or Concentration by the Total
gravimetric methods using a two-step heating cycle are also Evaporation Method Using a Thermal Ionization Mass
satisfactory (1, 2).2 The method presented in this test method is Spectrometer
a two-step heating cycle method. This test method is applicable D1193 Specification for Reagent Water
to sintered MOX pellets containing up to 10 weight percent D1356 Terminology Relating to Sampling and Analysis of
PuO2. Atmospheres
2.2 ISO Standards:4
1.2 The values stated in SI units are to be regarded as
ISO 21484 Nuclear Fuel Technology – Determination of the
standard. No other units of measurement are included in this
O/M Ratio in MOX Pellets – Gravimetric Method – First
standard.
Edition
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 3. Terminology
responsibility of the user of this standard to establish appro-
3.1 For definitions of terms used in this test method but not
priate safety and health practices and determine the applica-
defined herein, refer to Terminology C859.
bility of regulatory limitations prior to use.
3.2 Definitions of Terms Specific to This Standard:
2. Referenced Documents 3.2.1 average of the relative atomic mass—the weighted
2.1 ASTM Standards:3 average of the relative atomic mass of an element calculated as
C698 Test Methods for Chemical, Mass Spectrometric, and a function of its isotopic composition.
Spectrochemical Analysis of Nuclear-Grade Mixed Ox- 3.2.2 mole fraction—the ratio of the number of molecules
ides ((U, Pu)O2) (or moles) of a compound or element to the total number of
C753 Specification for Nuclear-Grade, Sinterable Uranium molecules (or moles) present (Terminology D1356).
Dioxide Powder 3.2.3 MOX—nuclear fuel composed of a mixture of uranium
C757 Specification for Nuclear-Grade Plutonium Dioxide and plutonium oxides ((U, Pu)O2).
Powder, Sinterable 3.2.4 O/M—ratio of the oxygen atoms divided by the metal
atoms in the sample.
1
3.2.5 relative atomic mass—a dimensionless physical
This test method is under the jurisdiction of ASTM Committee C26 on Nuclear
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of quantity, the ratio of the average mass of atoms of an element
Test. (from a single given sample or source) to 1⁄12 of the mass of an
Current edition approved Jan. 15, 2016. Published February 2016. Originally atom of carbon-12 (known as the unified atomic mass unit).
approved in 2015. Last previous edition approved in 2015 as C1817 – 15. DOI:
10.1520/C1817-16. 3.2.6 scavenging—the process of pushing a gas out by
2
The boldface numbers in parentheses refer to a list of references at the end of introducing a fresh flow in.
this standard.
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
4
Standards volume information, refer to the standard’s Document Summary page on Available from International Organization for Standardization (ISO), 1, ch. de
the ASTM website. la Voie-Creuse, CP 56, CH-1211 Geneva 20, Switzerland, http://www.iso.org.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 C1817 − 16
3.2.7 sintering—to increase the bonding in a mass of pow- 6. Interferences
der or a compact by heating below the melting point of the 6.1 Impurities in the sample may lead to inaccuracies in the
main constituent. determination of O/M ratios either due to loss of volatiles or
4. Summary of Test Method gain due to redox reactions. Even inert impurities present in
sufficiently high amounts compromise the accuracy of O/M
4.1 The purpose of the analysis is to test the stoichiometry
ratios because the true mass of the ((U, Pu)O2) subjected to the
of the MOX pellet by the determination of the O/M ratio. The
oxidation-reduction process remains unknown. When purified
principle of the method is that one or a number of MOX pellets
PuO2 and UO2 powders with maximum total impurity contents
are heated under a specific set of atmospheric conditions in
specified in Specifications C753 and C757 are used, the change
order to add or subtract oxygen molecules to the MOX pellets.
in mass due to the non-volatile and volatile impurities is
This process results in an O/M ratio of 2 in the MOX pellets
insignificant to the method. This method assumes that the
after heating. The mass of the oxygen molecules added to or
requirements of these two standards are met and therefore does
subtracted from the MOX pellets to achieve an O/M ratio of 2
not take into account the impact of impurities. If impurity
is quantified by weighing the MOX pellets before and after the
contents are higher than those specified in Specifications C753
heating step. Once the difference in mass is known, the number
and C757, an evaluation should be performed to determine
of atoms of oxygen added to or subtracted from the MOX
their impact on the method. This test method assumes that
pellets can be determined. The resulting data are used to
pellets are sintered. It does not correct for moisture or volatile
calculate the O/M ratio in the pellets prior to heating.
additives as the content of these impurities is negligible after
4.2 Three or four MOX pellets are weighed before and after sintering.
an oxidation-reduction heat treatment at specified time and
6.2 The crucibles if not clean can be a potential interference.
temperature intervals.
If necessary, the crucibles are cleaned and fired before use as
4.3 The heating and atmospheric conditions required to described in 10.1. If crucible cleanliness is tracked and if
achieve an O/M ratio of 2 in the MOX pellets are as follows crucibles are cleaned when necessary, the potential for the
(3-5): crucibles to be a source of interference is insignificant.
(1) Oxidation of the pellets in a current of air at 900 6
6.3 If crucibles are made from materials that oxidize under
20°C to increase the O/M ratio. There is no evidence that
the test conditions, they may prevent proper equilibration of
oxygen can be absorbed interstitially by plutonium dioxide to
the stoichiometry of the sample by consuming available
produce hyperstoichiometric oxide containing plutonium ions
oxygen. In addition, they would change weight and would
having a valency higher than four. On the contrary, uranium
impact the difference in mass calculation. This method assumes
oxide can be hyperstoichiometric.
that the crucible is made out of a material that is inert under the
(2) Reduction of the pellets in a stream of argon/hydrogen
test conditions, such as platinum alloyed with 20 % rhodium.
gas at 900 6 20°C to reduce the O/M ratio to 2. Under these
conditions (temperature and reducing atmosphere), the O/M 6.4 Weighing accuracy of the samples is critical to the
ratio is adjusted to 2. The choice of these parameters is based method. If the balance meets the specification in 7.1, is
upon a compromise between selecting a temperature low calibrated in accordance with manufacturer’s guidance, and is
enough to prevent reduction of plutonium oxide to a hypostoi- checked by procedure, the potential for the balance to be a
chiometric state but high enough to reduce hyperstoichiometric source of error is insignificant.
uranium oxide to UO2. 6.5 Loss of weight due to pellet chipping would invalidate
NOTE 1—The O/M ratio increases during the cooling process after the the analysis. Handle pellets with care.
heat cycles described above unless it is done under Ar or Ar/H2 6.6 The average of the relative atomic mass of the uranium
atmosphere. So, control of the cooling atmosphere is needed.
and plutonium in the samples impacts the accuracy of the
4.4 The reactions involved are: calculation. The average of the relative atomic mass of uranium
~ U , P u ! O 26x 6x⁄2O 2 → ~ U , P u ! O 21x (1) and plutonium are measured by Thermal Ionization Mass
~ U , P u ! O 21x 1xH 2 → ~ U , P u ! O 2.0001xH 2 O (2) Spectrometry (TIMS) in accordance with Test Method C1672
and this measured value is accounted for in the calculation.
4.5 The calculation of the stoichiometry is based on the
weight difference of the pellets before and after heat treatment 7. Apparatus
and the mean atomic mass of the heavy metals in the MOX 7.1 Analytical Balance, with precision 60.1 mg.
pellets (see Section 11 for details of the calculation).
7.2 Tube Furnace, capable of controlling temperatures 900
5. Significance and Use 6 20°C and fitted with a fused quartz tube chamber which
5.1 MOX is used as a nuclear-reactor fuel. This test method allows for sweeping the chamber with various gasses.
is designed to determine whether the O/M ratio meets the 7.3 O/M Apparatus—See Fig. 1. This apparatus is not
requirements of the fuel specification. Examples for establish- typically commercially available and users of this test method
ing a fuel specification are given in Specification C833. must build a similar device.
5.2 This method is suitable for all sintered MOX pellets NOTE 2—It is important that the thermocouple be located such that it
containing up to 12 weight % PuO2 when the UO2 and PuO2 can monitor the temperature in the zone in which the sample is placed, or
meet the requirements of Specifications C753 and C757. can be calibrated to account for any physical offset. It is also important

2
 C1817 − 16

FIG. 1 O/M Apparatus

that the furnace is designed so that the temperature remains stable across 8.1.3.1 Flow rate: 16 litres/hour.
the region in which the sample is placed. For safety reasons, it is important 8.1.3.2 Pressure: 200 kPa.
to ensure that the design of the furnace limits the possibility of mixing air
with the hydrogen/argon gas mixture. 8.2 Liquid Reagents:
7.4 Platinum sample crucibles—alloyed with 20 % rho- 8.2.1 Water (if using cleaning method 2)—Unless otherwise
dium. indicated, references to water shall be understood to mean
7.5 Fused Quartz Boats (if needed), designed to hold laboratory accepted demineralized or deionized water in con-
multiple platinum sample crucibles if more than one sample is formance with Specification D1193, Type 1.
measured at the same time. 8.2.2 Nitric Acid (if using cleaning method 2)—(16 M
HNO3) concentrated, specific gravity 1.42.
7.6 Pair of Stainless Steel Tweezers. 8.2.3 Nitric Acid 7M (if using cleaning method 2)—Add 440
7.7 Pair of Tongs (if using cleaning method 2 described in mL of concentrated HNO3 to 900 mL of DI water, dilute to a
10.1). final volume of 1 litre.
7.8 Hot Plate (if using cleaning method 2 described in 8.3 Reference Materials:
10.1). 8.3.1 There are no certified reference materials (MOX
7.9 Beaker (if using cleaning method 2 described in 10.1). pellets) for the O/M ratio determination by the thermogravi-
metric treatment method (6).
7.10 Gas Flow Meter, Pressure Gauge, and Regulator.
8. Reagents and Materials 9. Precautions
8.1 Purge Gases: 9.1 Because of the toxicity of plutonium, all operations
8.1.1 Argon—Certified 99.995 % purity (O2 <5 mg.kg-1, should be performed within an approved glove box fitted with
H2O <5 mg.kg-1, N2 <20 mg.kg-1). appropriate filters to contain any small particle of plutonium. A
8.1.1.1 Flow rate: 16 litres/hour. detailed discussion of the necessary precautions is beyond the
8.1.1.2 Pressure: 200 kPa. scope of this test method. Personnel involved in these analyses
8.1.2 Air—Filtered and dried (Suggested air treatment sys- should be familiar with safe handling practices (7, 8).
tem features: filter efficiency ≥98 % of 0.01 µm, dew point
9.2 The furnace, sample tube, and sample crucibles are
≤20°C, total hydrocarbons ≤5 mg.m-3).
heated to 900 6 20°C. Extreme care must be exercised to avoid
8.1.2.1 Flow rate: 12 litres/hour.
burns or injury by quartz in a glove box and to avoid breaching
8.1.2.2 Pressure: 200 kPa.
the primary confinement boundary.
8.1.3 Argon/Hydrogen Mixture—Certified 99.995 % purity
with the total amount of impurities (O2 + H2O + CnHm) <10 9.3 Exercise appropriate caution when working with com-
mg.kg-1. The gas mixture shall be (5 % <H2 <7 %). pressed gases.

3
 C1817 − 16
9.4 Hydrogen is explosive when mixed with oxygen in the 10.1.2.11 Remove the crucibles (crucibles in the quartz boat
presence of an ignition source. Using a mixture of argon and if necessary) from the furnace using a pair of tweezers, shut off
hydrogen instead of pure hydrogen, limiting the hydrogen the argon and allow the crucibles to cool to less than 35°C.
content to a maximum of 7 % and ensuring that the design of 10.1.2.12 Weigh each crucible to within 60.1 mg. Record
the furnace does not allow for the hydrogen/argon mixture to the value as m0.
react with air limits the safety risk of this method. Using a 10.2 Weighing and Introduction of the Pellets:
glove box with an inert atmosphere also reduces the risk and 10.2.1 Using a pair of tweezers, place the pellets vertically
improves the method performance. into the empty crucible, and weigh to the nearest 0.1 mg.
Record the value as m1.
10. Procedure 10.2.2 Using a pair of tweezers, introduce the sample
10.1 Crucible Cleaning—The crucibles shall be clean and crucibles containing the pellets (crucibles in the quartz boat if
weighed before use. Cleaning prior to each use is not required, necessary) into the furnace and seal the furnace door.
but an evaluation of the cleanliness of the crucible is required. 10.2.3 Proceed with the oxidation.
Cleaning is required if dust is visible. If crucible cleaning is 10.3 Oxidation:
deemed required, the following are two examples of how the 10.3.1 Place the furnace under argon by introducing the
crucibles can be cleaned. argon gas at a pressure of 200 kPa and a flow rate of 16 L/h.
10.1.1 Example Cleaning Method 1: 10.3.2 Turn on the furnace.
10.1.1.1 Wipe out the empty crucible with disposable paper 10.3.3 Heat the pellets in the argon atmosphere at 900 6
or cotton wipes. 20°C for 5 min.
10.1.1.2 Introduce the crucible (crucibles in the quartz boat 10.3.4 After 5 min turn off the argon gas and introduce the
if necessary) into the furnace using a pair of tweezers and seal air at a pressure of 200 kPa and a flow rate of 12 L/h.
the furnace door. 10.3.5 Heat the pellets in the furnace for 1 min under air
10.1.1.3 Place the furnace under argon/hydrogen by intro- scavenging.
ducing the argon/hydrogen at a pressure of 200 kPa, and a flow 10.3.6 After 1 min turn off the air and introduce argon under
rate of 16 L/h. the conditions given in 10.3.1.
10.1.1.4 Turn on the furnace. 10.3.7 Heat the pellets in the argon atmosphere for 5 min.
10.1.1.5 Heat the crucibles at 900 6 20°C for 1 h. 10.3.8 This completes the oxidation cycle, turn off the argon
10.1.1.6 Shut off the furnace and allow the crucible to cool and quickly initiate the reduction sequence.
to less than 150°C in the argon-hydrogen atmosphere within 10.4 Reduction:
the furnace. If the glove box atmosphere is inert, the crucibles 10.4.1 Place the furnace under argon/hydrogen by introduc-
can be removed at a higher temperature. ing the argon/hydrogen at a pressure of 200 kPa and a flow rate
10.1.1.7 Remove the crucibles (crucibles in the quartz boat of 16 L/h.
if necessary) from the furnace using a pair of tweezers, shut off 10.4.2 Heat the pellets under argon/hydrogen scavenging at
the argon-hydrogen and allow the crucibles to cool to less than 900 6 20°C for 8 hours.
35°C. 10.4.3 After the eight hour time period, shut down the
10.1.1.8 Weigh each crucible to within 60.1 mg. Record the furnace and allow the pellet samples to cool to 50°C or less
value as m0. under argon/hydrogen scavenging. This completes the reduc-
10.1.2 Example Cleaning Method 2: tion cycle.
10.1.2.1 Wipe out the empty crucible with disposable paper 10.4.4 Remove the crucibles (or crucibles in the quartz boat)
or cotton wipes. from the furnace tube using a pair of tweezers and allow them
10.1.2.2 Place the crucibles in a beaker with enough 7M to cool to 35°C or less. Turn off the argon-hydrogen.
HNO3 to completely cover the crucibles. 10.4.5 Initiate the weighing sequence as quickly as practical
10.1.2.3 Place the beaker containing the crucibles onto a hot after the crucibles have cooled down.
plate and boil the acid for approximately 30 min.
10.5 Weighing:
10.1.2.4 Allow the acid solution to cool and remove the
10.5.1 Weigh each platinum sample crucible containing the
crucibles using a pair of tongs.
MOX pellets as quickly as practical to the nearest 0.1 mg.
10.1.2.5 Rinse the crucibles with deionized water in confor- Record the final mass of the crucible as m2.
mance with Specification D1193, Type 1.
10.1.2.6 Introduce the crucibles (crucibles in the quartz boat 11. Calculation
if necessary) into the furnace using a pair of tweezers and seal
the furnace door. 11.1 Calculation of the Average Atomic Mass:
10.1.2.7 Place the furnace under argon by introducing the 11.1.1 Calculate the average atomic mass of the heavy metal
argon at a pressure of 200 kPa, and a flow rate of 16 L/h. oxide after heat treatment, assuming that the O/M ratio equals
10.1.2.8 Turn on the furnace. exactly 2, using the formula:
10.1.2.9 Heat the crucibles at 150°C for approximately 30 @ A t ~ P u ! # 3 Pu%1 @ A t ~ U ! # 3 U%1 @ A t ~ A m ! # 3 Am%
At 5 12
min. Pu%1U%1Am%
10.1.2.10 Shut off the furnace. 3 At ~ 0 ! (3)

4
 C1817 − 16
where: NOTE 4—This calculation does not take into account metallic or volatile
impurities as they are considered negligible to the analysis, as discussed in
At = the average of the relative atomic mass of the 6.1.
heavy metal oxide,
At(Pu) = the average of the relative atomic mass of pluto- 12. Precision and Bias
nium in the oxide from a TIMS analysis,
12.1 Precision—The repeatability standard deviation (1σ) of
At(U) = the average of the relative atomic mass of uranium
the method as determined by a single laboratory has been
in the oxide from a TIMS analysis,
At(Am) = the average of the relative atomic mass of ameri- determined to be between 0.001 and 0.002 O/M units.
cium in the oxide (241Am), Typically, a repeatability of 60.004 O/M units (2 times the
Pu % = the mole fraction, in percentage, of plutonium in standard deviation) is sufficient to measure the O/M ratio and
the oxide, verify that it meets the specification for MOX fuel. This
U% = the mole fraction, in percentage, of uranium in the thermogravimetric method, if performed as specified, meets
oxide, this requirement. The reproducibility of this test method is not
Am % = the mole fraction, in percentage, of americium in provided at this time because very few laboratories perform
the oxide, and this analysis. In addition, the cost and complexity of the
At(O) = the atomic mass of oxygen (15.9994). logistics associated with the transfer of MOX pellets between
laboratories is considered to be prohibitive. As a result, it is not
NOTE 3—The measurement method for determining the mole fraction
of americium in the oxide is not described in this standard. It can be
likely that reproducibility data will be available in the future. If
measured using a suitable method, standardized or qualified internally by any user is aware of repeatability data from other laboratories,
the laboratory using guidance in Guide C1068. please contact the technical committee having jurisdiction over
11.2 Calculation of the O/M Ratio: this standard, and those data will be considered for future
11.2.1 Calculate the O/M ratio as follows: versions of the standard.
A t 3 ~ m 2 2 m 1! 12.2 Bias—The bias of the test method cannot be tested
O⁄M 5 2.000 2 (4) reliably because of the lack of suitable reference or calibration
A t~ O ! 3 ~ m 2 2 m 0!
materials. The absence of bias depends upon quantitative
where: conversion of the sample to the stoichiometric dioxide. The
m0 = the mass, in grams, of the empty crucible, conditions of analysis were selected on the basis of thermody-
m1 = the mass, in grams, of the crucible with test sample namic data to ensure complete conversion to the stoichiometric
before oxidation-reduction, dioxide and therefore the bias does not have a significant
m2 = the mass, in grams, of the crucible with test sample impact on the uncertainty of the method.
after oxidation-reduction heat treatment,
At(O) = the relative atomic mass of oxygen (15.9994), and 13. Keywords
At = the average of the relative atomic mass of heavy 13.1 gravimetry; MOX; oxygen to metal (O/M) ratio; plu-
metal oxide calculated from Eq 3. tonium; thermal analysis; uranium

REFERENCES

(1) Urie, M. W., Burt, M. C., and Delvin, W. L., “A Comparison of (5) Lyon, W. L., “The Measurement of Oxygen to Metal Ratio in Solid
Thermogravimetric Methods Used to Determine Oxygen-to-Metal Solutions of Uranium and Plutonium Dioxides,” USAEC Rep. GEAP
Ratios in Mixed-Oxide Fuels,” Hanford Engineering Development 4271, 1963.
Laboratory Report HEDL-TME-72-56, April 1972. (6) Rubin, J., Chidester, K., and Thompson, M., “O/M Ratio Measure-
(2) McNeilly, C. E., and Chikalla, T. D., “Determination of Oxygen/ ment in Pure and Mixed Oxide Fuels – Where Are We Now?,” Los
Metal Ratios for Uranium, Plutonium, and (U, Pu) Mixed Oxides,” Alamos National Laboratory, LA-UR-00-5805, 2000, http://lib-
Journal of Nuclear Materials, Vol 39, No. 1, pp. 77–83, 1971. www.lanl.gov/la-pubs/00357110.pdf.
(3) Brett, N. H., and Russell, L. E., “The Sintering Behaviour and (7) American Standards Association Inc., Sectional Committee N6 and
Stability of (Pu,U)02 Solid Solutions,” Trans. Br. Ceram. Soc., Vol 62, American Nuclear Society Standards Committee, Nuclear Safety
No. 2, p. 97, 1963. Guide, USAEC Report TID-7016 (Rev. 1); AERDB, Goodyear
(4) Russell, L. E., Brett, N. H., Harrison, J. D. L., and Foster, E., “The Atomic Corp., 1961.
Fabrication of Fuel Pellets from Mixed UO2 and PuO2 Powders,” (8) Wick, O. J., Ed., Plutonium Handbook, Gordon and Breach Science
UKAEA Rep. AERE-R 3429, 1960. Publishers, Vol II, 1967.

5
 C1817 − 16
ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/