ROLE OF ANALYTICAL CHEMISTRY IN THE

DEVELOPMENT OF NUCLEAR FUELS

Power point presentation prepared by
KL Ramakumar
India

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 Analytical chemistry in nuclear fuel cycle
- indispensable
- pivotal role in the entire nuclear fuel cycle
- ore refining
- conversion
- nuclear fuel fabrication
- reactor operation
- nuclear fuel reprocessing
- waste management

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 Chemical Quality Control

Chemical quality control provides a means to ensure that

the quality of the fabricated fuel conforms to the chemical
specifications for the fuel laid down by the fuel designer
The specifications are worked out for the major and minor
constituents which affect the fuel properties and hence its
performance under conditions prevailing in an operating
reactor.
Each fuel batch has to be subjected to comprehensive
chemical quality control for trace constituents,
stoichiometry and isotopic composition.

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 Why is CQC needed?
Control of uranium and plutonium contents and their
isotopic compositions is essential in order to ensure
the required fissile content
O/M can affect thermal conductivity, melting point,
number of phases, chemical reactivity and mechanical
strength. O/M has to be maintained in the specified
limits of hypostoichiometry since the oxygen potential
significantly increases with irradiation which may lead
to clad corrosion
Control of trace constituents in the fuel is necessary
to obtain the designed burn-up

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 Why is CQC needed?

Fluorine, chlorine and moisture cause corrosion of

the clad

Moisture can modify the O/M of the fuel and also

release hydrogen which can cause pressure buildup

Carbon can react with oxygen forming gaseous

carbon monoxide which facilitates transfer of carbon
from fuel to the clad causing damage to it.

Boron, cadmium and rare earths affect the neutron

economy

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 Analytical methodology for chemical quality control
measurements

(1) preparation of starting materials

(2) Sampling methodologies
(3) Dissolution of samples
(4) Thorium, uranium and plutonium content
(5) Isotopic composition (for fissile and fertile content)
(6) Americium content
(7) Oxygen to metal ratio
(8) Trace metals determination
(9) Trace non-metals determination
(10)Total gas content
(11)Moisture content in the case of oxide fuels.

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A number of analytical parameters need to be
determined as a part of chemical quality control of
nuclear materials.
Classical to sophisticated instrumentation techniques
New superior methodologies
- reduction in the time of analysis
- improvement in the measurement precision
and accuracy
- simplicity of the technique itself
- ease of automation

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 STARTING MATERIALS (UO2 or PuO2)

UO2: Direct denitration, ammonium diuranate (ADU), ammonium

uranyl carbonate (AUC), or peroxide precipitation followed by
subsequent conversion to UO2.

ADU precipitation conditions decide particle size and

agglomerates

ADU is converted to UO3 powder by calcination at about 3000C,

reduced to UO2 with cracked ammonia at about 6500C.

It is stabilized by partial oxidation to UO2.15 using CO2 or

controlled amount of air.

The particle size of powder is controlled within 2-10µm by ball

milling and a surface area of 5m2/g is considered optimum
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PuO2: Precipitation as plutonium(IV) oxalate is the most
widely used commercial method of converting plutonium
nitrate solution to dioxide as it offers both purification as well
as better handling properties of the final product.

Pu(III) oxalate precipitation and subsequent calcination can also

be used.
Plutonium is adjusted to trivalent state, by the addition of 1M
ascorbic acid, in the presence of an oxidation inhibitor such as
hydrazine. Finally the precipitate is calcined at 700ºC to obtain
PuO2

Addition of excess of oxalic acid reduces the solubility of the

product (minimises loses).

Oxalate is decomposed to oxide

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 MOX fuel: 3 main routes
1. AU/PuC process (Ammonium Uranyl-Plutonyl Carbonate):
AU/PuC complex is precipitated by adding ammonia and carbon
dioxide to a solution of uranium nitrate and plutonium nitrate followed by a
calcination step
2. Micronizing method:
PuO2 powder is micronized with UO2 powder to form a “master blend”.
This is mechanically mixed with free flowing AUC or ADU (Ammonium Di-
Uranate) UO2 to obtain the specific plutonium content required. The very close
contact between UO2 and PuO2 aggregates allows for sufficient inter-diffusion
during sintering.
3. SBR (short binderless route):
Homogenisation is attained by means of a high- energy attritor
mill, which blends the oxide powders and a spherodizer in order to
condition the powder to granules prior to pressing and sintering. At the
milling stage, suitable lubricant and pore former are added in order to
control the pellet density and obtain desired characteristics.

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MOX Fuel:
Microwave heating method can also be used as a preparation
route for MOX fuel production.

U/Pu nitrate solution is heated by microwaves and co-converted

to (U,Pu)O2 powder.

- Heating of the U/Pu nitrate solution to its boiling point

- Concentrate by vaporization
- De-nitration by decomposition of the molten nitrate
mixture and formation of de-nitrated cake
- Stabilization of the de-nitrated cake.

(U,Pu)C:
Monocarbide phase with a small admixture of M2C3. This fuel is
fabricated by the carbothermic reduction of a mixture of the
oxides of uranium and plutonium.
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Analytical Chemistry in Dissolution of refractory Oxides
and Carbides

One of the most widely used methods of dissolution is to

treat the sample with concentrated HNO3 and small
quantities of HF. The dissolution rate generally
decreases with increase in Pu/U ratio.

Fusion with ammonium bisuiphate and later treatment

with H2SO4

Sealed tube method in which a mixture of sample and

concentrated acids is subjected to high pressure (4000
psi) at a ternperature of 350°C. (safety precautions with
plutonium samples!)

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(U,Pu)C: Conventionally carbide is converted to oxide
which can be dissolved using the oxide dissolution
procedure.
A direct dissolution method by refluxing the sample in 1:1
HNO3-H2SO4 mixture eliminated the oxide conversion step
reducing the overall time required for dissolution.

Alloy fuels like U-Zr are dissolved using 3M HNO3-1% 1M

HF by heating at 800C for 4 hrs.

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Analytical Chemistry in Thorium, Uranium, and Plutonium
Determination
Thorium: Classical EDTA complexometric titration
method.
Pu interference could be eliminated by
preferentially oxidizing it Pu (VI) by AgO prior to
titration.
EDTA titration with potentiometric end point detection
using Fe(III)/Fe(II) couple.
Elimination of personal bias in the volumetric titration
using xylenol orange as indicator for end point detection.

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 Electroanalytical Chemistry (Multiple oxidation states)
Titration of Plutonium
1) Pu + Ag(II) --------------- Pu(VI) + Ag(II) excess
2) Ag(II) excess --------------- Ag(I) using sulfamic acid
3)Pu(VI) + 2Fe(II) --------------- Pu(IV) + 2Fe(III) + Fe(II) excess
4) 2Fe(II) + Cr(VI) --------------- 2Fe(III) + Cr(IV)
Titration of Uranium
UO2++ + 2Fe++ + 4H+ -------- U4+ + 2Fe3+ + H2O
Fe++ + NO3- + 2H+ -------- Fe3+ + NO2 + 2H2O
U4+ + 2VO++ ------------ UO2++ + 2V3+
Cr2O7-- + 6V3+ + 2H+ ------------ 2Cr3+ + 6VO++ + 2H2O
Cr2O7-- + 3U4+ + 2H+ ------------ 2Cr3+ + 3UO2++ + 2H2O
15
 U determination in presence of Pu and Fe

Ti(III) is used as the reductant in a mixture of H2SO4 and

HNO3. Fe(II) and Pu(III) are selectively oxidized by the
nitrous acid generated in the reaction between Ti(III) and
HNO3.

The U(IV) is determined by titration with K2Cr2O7 using

biamperometry to detect the end point.

The method is applicable to a variety of nuclear materials

encountered at different stages of the nuclear fuel cycle and
has no bias.
The precision of the method is evaluated at different levels
from 100 microgram to 100 milligram. The method is
simple, rapid and convenient.
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 Controlled potential coulometric method for U

Reduction of uranium in 8M H2SO4 by Ti(III) followed by

destruction of excess Ti(III) and selective oxidation of Fe(II)
or Pu(III) to Fe(III) or Pu(IV), respectively, by sodium
nitrite.

U(IV) is subsequently determined by electrolytic oxidation at

Pt electrode using Fe(III) as an intermediate.

The precision obtained for uranium results was ±0.25%.

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The major technique applied is the Davies and Gray
potentiometric titration, which is applied in its original
NBL-modified form or in a robotized automate set-up
using a scaled-down version. Both variants deliver
routinely results with a precision and accuracy below
0.05% relative (standard deviation).

Propagating all uncertainty components, including

systematic uncertainties of calibration and certified values
of primary reference materials, the total uncertainty for
routine sample results (mean of two dissolutions and
titrations) is estimated as ±0.07% relative (95% confidence
interval).

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 Pu determination
Reductimetric titration of Pu(VI) to Pu(IV) using the
reductant Fe(II)
as titrant with amperometric detection of the end point
after preliminary oxidation of the Pu to Pu(VI) using
excess Ag(II) oxide as an oxidant.
Random errors of 0.1 -0.2% are generally attained.
Systematic errors are usually better than 0.1%.
Random errors under the best conditions are better than
0.05%.

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 Controlled Potential Coulometry of Pu

Quantitative electrolytic oxidation of Pu(III) to Pu(IV) at an electrode

maintained at a controlled potential with determination of the quantity
of Pu from the quantity of electricity required for the complete
oxidation.

Random and systematic errors of 0.1%

SAMPLE SIZE: 1 - 10 mg Pu
SAMPLE TYPES: Pu metal, oxides, Mixed U, Pu oxides, Pu nitrate
solutions, Dissolver solutions Applicable to most Pu materials when
ion-exchange separation is used.

ADVANTAGES: Absolute method. High precision and accuracy on

relatively small quantities of Pu. Relatively free of interferences.
Readily automated. Adaptable to remote operations and analysis of
irradiated materials.
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 Other Specifications

Specification Methodology
Isotopic composition TIMS,Alpha spectrometry
NDA techniques
Pu in finished fuel pins NDA technique

Pu-238 and Am-241 Alpha spectrometry

Total gas content Vacuum extraction

Moisture content Carbides: should not be present

Manometry or coulometry
O/M Thermogravimetry, EMF and
gas equilibration

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 Scope for further improvements
Necessitated by
New and advanced nuclear fuels
Nitrides/carbides: (Pu0.07Zr0.93)N, (U,Pu,MA)C, U,Pu,MA)N
CerCer / CerMet: Mo - (Pu0.8Am0.2)O2
Particle Fuels for VHTR: (Zr,Y,Pu)O2

Precision and accuracy requirements (from CQC and NUMAC)

Automated instrumentation
New simplified multi-task capabilities

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Determination of microamounts of plutonium isotopes by
luminescent radiation in the infra-red region of PbMoO4
crystallophosphors activated by plutonium is proposed. The
determination is possible against the background of
subtantial amounts of uranium, iron, rare earths and other
elements. The detection limit of plutonium is 10–9 g in the
samples tested. The accuracy is 0.1 for a confidence level of
0.95.

Yu. P. Novikov, V. B. Gliva, S. A. Ivanova and

B. F. Myasoedov, J. Radioanal. Nucl. Chem., 103, 337(1986)

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Techniques that use atomic emission for element detection
and quantification encounter a large number of spectral
interferences when analyzing plutonium samples due to the
numerous emission lines of plutonium.
Mass spectrometric techniques do not have that problem. In
ICP-MS the main effect plutonium has on the elemental
determinations is a signal suppression. With matrix dilution
and signal normalization that problem is mitigated.

The typical routine sample requires an acid digestion with a

combination of nitric, hydrochloric, and hydrofluoric acids. The
digested sample is split into a portion for ICPMS analysis, and
a portion for ICP-AES analysis. Prior to the ICP-AES analysis,
ion chromatography is used to remove the plutonium from the
samples.

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 GDMS in nuclear technology

Direct current GDMS applied to conducting and non-

conducting nuclear samples.
For the non-conducting oxide-based nuclear samples the
relative sensitivity factors (RSFs), applied for quantitative
analysis, are affected by the oxygen content in the matrix.
For these samples the effect of getter metals, such as
tantalum and titanium as binder material are used.

Metallic alloys were analysed using several analytical

techniques. The GDMS results obtained applying RSFs from
the major metallic element uranium were in agreement with
those from independent techniques, such as titration,
thermal ionization MS and ICP-MS
Maria Betti, J. Anal. At. Spectrom., 11, 855(1996)

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 A Rapid method for O/M in MOX

The sample and the nickel metal were fused in a graphite crucible in a
resistance heating furnace under helium flowing through the system.

The oxygen in the MOX fuel reacted quantitatively with the crucible
graphite producing carbon monoxide in proportion to oxygen content.

CO intensity measured using non-dispersive infrared

spectrophotometry (NDIR).

Good agreement with the thermogravimetric values.

The relative standard deviation was < 0.20%
Only 30 mg of sample required
Analysis time takes about 10 min
Applicable over a wide range of plutonium contents

T. Hiyama, Anal. chim. Acta, 402, 297(1999)

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Specification Methodology in 1970s Methodology currently
(*) in use
Carbon Manometry, IGF-TCD
conductometry
Chlorine and fluorine Pyrohydrolysis and Pyrohydrolysis and ion
spectrophotometry/ISE chromatography
Nitrogen Kjeldahl distillation Kjeldahl distillation
and Nessler’s method and indophenol blue
method
IGF-TCD
Ion chromatography
Phosphorus Spectrophotometry Ion chromatography
and spectrophotometry
Sulphur Spectrophotometry Combustion
extraction-QMS
(*)M . V. Ramaniah in Pure & Appl.Chem., 54, 889 (1982)

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Specification Methodology in Methodology
1970s (*) currently in use

Trace elements Carrier ICP-OES, ICP-

distillation DC- MS
Arc AEC HPLC, ion
AAS chromatography

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 Periodic performance assessment of the analytical
methodologies

Necessary for CBMs, Safeguards evaluation

Proficiency testing
Intercomparisoon experiments
Sample exchange programmes

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Uranium analysis by Davis Gray Method
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Pu analysis assessment

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 Control Limits
Method Measurand
material Control Warning
Gamma NBS020 235U (Wt%) 0.50 0.33
Spectrometry NBS030
241Am 1.97 1.47
238/239 3.56 2.66
HRGS NBS947,
SAL9984 240/23 1.93 1.46
241/239 1.50 1.13
Alpha NBS947, Activity ratio 1.17 0.85
Spectrometry AEA90099

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 Limits
Method
Control
Measurand
material Control Warning
McD&S UK-Pu-1 Pu conc. 0.23 0.17
(as control
material)
D&G Pu- EC-110 U conc. 0.26 0.19
Lab
D&G U- EC-110 U conc. 0.12 0.09
Lab

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 limits
measurand
control
Method control warning
material

LSD Pu conc. 0.41 0.31

control
IDMS LSD
U conc 0.22 0.17
UK82522
Pu conc.
or mixture
0.48 0.36

NBL112A
IDMS
(NBS960) U conc
product
0.43 0.30
or mixture

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 Limits
Measurand
Control
Method
material Control Warning
240/239
NBS947
0.19 0.14
242/239 0.51 0.38
240/239
UK-Pu-3
0.11 0.085
242/239 0.21 0.16
UK-Pu-4 240/239 0.18 0.13
MassSpec
240/239
Pu
0.18 0.13
UK-Pu-5 242/239 0.32 0.23
244/239 0.36 0.27
UK-Pu-6 240/239 0.15 0.11
NBL-128 242/239 0.20 0.15
CBNM-047a 244/239 0.30 0.22

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 Measurand
Control Limits
Method
material
Control Warning
NBS010 235/238 0.36 0.27

NBS020a,
235/238
0.15
NBS030a
0.20

NBS100 to
NBS930

MassSpec U
NBL116, 235/238 0.22 0.16
GUS3568,
CBNM-
072/2
CBNM-
072/2, 233/238 0.26 0.20
GUS3568
GUS3568 236/238 0.15 0.11

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 MATERIAL TYPE and METHOD UNCERTAINTY OF ROUTINE
ANALYSIS RESULT (95%
CONFIDENCE INTERVAL,
relative)
U Assay U Products (D&G titration) ±0.07 %

U Assay U/Pu Products (D&G) ±0.15 %

U Assay U/Pu Products (IDMS) ±0.21 %

Pu Assay U/Pu Products (McD&S) ±0.14 %

Pu Assay U/Pu Products (IDMS) ±0.26 %

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 MATERIAL TYPE and METHOD UNCERTAINTY OF ROUTINE
ANALYSIS RESULT (95%
CONFIDENCE INTERVAL, relative)

U Isotopic [wt% 235U], natural U ±0.27 %

U Isotopic [wt% 235U], LEU ±0.12 %
U Isotopic [wt% 235U], HEU ±0.09 %
U Isotopic [wt% 235U], LEU, gamma- ±0.26 %
Spec
Pu Isotopic wt% 239Pu ±0.03 %
Pu Isotopic wt% 240Pu ±0.13 %
Pu Isotopic wt% 241Pu ±0.75 %
Pu Isotopic wt% 242Pu ±0.37 %
Pu Isotopic wt% 238Pu, alpha-spec ±0.84 %
241Am by HRGS/MGA ±1.47 %

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 Standard reference materials
Required to
(1) calibrate analytical methods
(2) evaluate the capabilities of analysts and
(3) assure the reliability of routine measurements.
Commercially available only for uranium and plutonium contents
(chemical) and their isotopic composition (isotopic).
Not accessible to India
Indigenous efforts to prepare and characterise reference materials for
thorium, uranium and plutonium.
BARC has prepared rubidium uranium Sulphate and potassium
plutonium Sulphate reference materials for U and Pu contents
respectively.
BARC-NFC inter comparison experiments: for characterising U3O8
and ThO2 samples as reference materials for trace elements.

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 Conclusions
There are many areas in nuclear reactor fuel technology
where analytical chemistry plays a crucial role like fuel
manufacture, irradiation behaviour and reactor safety.
CQC is an integral and indispensable component in
nuclear technology.
A wide gamut of analytical methodologies is required for
the chemical quality control measurements on nuclear
materials.
Analytical chemists constantly strive to develop new
analytical methodologies to address many issues in
nuclear technology.

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