Leading Thermal Analysis

Analyzing & Testing

Characterization of Nuclear Materials
Methods, Instrumentation, Applications
2
Introduction
The world demand for electricity is
projected to double by mid-century.
Because of the ever-increasing price
of fossil fuels and the associated
environmental concerns such as carbon
dioxide emissions, nuclear power
generation is regaining popularity.
Nuclear fuel is clean and relatively
inexpensive compared to fossil fuels.
It is in fact the only source of clean,
sustainable and affordable energy
which can meet current and near-term
demands for electricity generation,
if sufcient numbers of reactors of
current and advanced design can be
brought on line in a timely manner.
In addition, the nuclear reactors of
current design are safe and, save a
natural disaster such as the magnitude
9 earthquake east of Japan and
resulting tsunami, accidents are highly
unlikely. In spite of the accident at the
Fukushima nuclear power plant caused
by the earthquake/tsunami, the strong
resurgence so-called renaissance of
nuclear power is expected to continue.
This renaissance has led to the
formation of a multi-national
cooperation called the Global Nuclear
Energy Partnership (GNEP). Two of the
stated aims of GNEP are to:
3
Time line for reactor development
Generation I
Early Prototype
Reactors
I II III III
+
IV
1950 1960 1970 1980 1990 2000 2010 2020 2030
Generation II
Commercial Power
Reactors
LWR-PWR, BWR
CANDU
AGR
Generation III
Advanced LWRs
Generation III
+
Evolutionary
Designs Offering
Improved
Economics
for Near-Term
Deployment
Generation IV
Highly
Economical
Enhanced Safety
Minimal Waste
Proliferation
Resistant
develop a new generation of nuclear
power plants the so-called Genera-
tion IV systems (GEN IV) in which
six different reactor types are under
consideration (both thermal and fast
reactors), and
reduce waste by recycling used
nuclear fuel using new technologies.
The history of commercial nuclear power
generation reaches back to the mid-60s.
The Generation III+ reactors now under
development and the GEN IV reactors
under consideration are of unique design
with respect to safety, performance and
economics. The GEN IV reactors include
the Very High Temperature Reactor
(VHTR), the Sodium-cooled Fast Reactor
(SFR) and perhaps the most unique, the
Molten-Salt Reactor (MSR). Many of
these reactors will contain unique fuel
systems and reactor materials.
4
Introduction
The major concern with nuclear power
generation today is the safe disposal of
used fuels. Because of storage-related
problems, recycling of used fuel is of
paramount importance. Fuel recycling
is not a new concept. In fact, used fuel
from light-water reactors (LWR) has
been reprocessed into (U,Pu)O
2

so-called MOX fuel for some time by
various countries. This is economically
feasible because spent fuel contains
not only ssion products and minor
actinides such as Americium, Neptunium
and Curium, but a large percentage of
ssile Uranium and Plutonium isotopes
as well. Composition of used fuel
U 95.6%
(
235
U 0.5-1.0%)
Stable Fission
Products
2.9%
Plutonium
0.9%
Cs and Sr
0.3%
Long-lived
I and Tc
0.1%
Minor
Actinides
0.1%
Other
Long-lived
Fission
Products
0.1%
Source: Idaho National Laboratory
5
Closed fuel cycle with front end processing of UO
2
and back end recycling/target fabrication
Reactor/
Power Plant
Interim
Storage
Geological
Repository
Fuel Recycle/
Target
Fabrication/
Separation
Reconversion
Enrichment
Conversion
Uranium
Mining & Milling
Fuel Fabrication
UO
2
Aged Used Fuel
Waste
(U,Pu,Np)O
2
(Am,Cm)O
2
UO
2
Fuel
UO
2
UO
2
Recycle
F R O N T E N D
B A C K E N D
Used
Fuel
UF
6
UF
6
U
3
O
8
It has been estimated that the effective
capacity of geological repositories can
be increased greatly if the long-lived
minor actinides such as those
mentioned above plus Pu (transuranics)
are separated and fabricated into the
reprocessed fuel or targets for
transmutation/consumption. Several
concepts have been proposed to realize
this, some of which utilize fast reactors
and others thermal reactors.
6
Introduction
In addition, studies have shown that
signicant reductions in repository heat
and radiotoxicity loads can be realized by
placing used fuel in interim storage for
a few years to allow short-lived ssion
products such as Cs-137 and Sr-90 to
partially decay prior to separation.
Interim storage also reduces the
problems associated with reprocessing
fuel containing Cm, but also increases
the content of high-vapor-pressure
Am-241 due to the -decay of Pu-241.

Of course, a prerequisite for the
successful design of any new reactor or
fuel system as well as modernization of
the existing reactor eet is the accurate
knowledge of the thermophysical
properties for the materials of interest.
This will necessitate the measurement
of the thermophysical properties for
fresh, reprocessed and used fuels as well
as irradiated and unirradiated reactor
component materials.
Assumptions
Burnup: 50 GWd/MT
Separation: 25 years
Emplacement: 25 years
Closure: 100 years
Limited by 200C
drift wall temp.
at emplacement
0.001
0.001
0.01
0.01
0.1
0.1
1
1
Limited by 96C
mid-drift temp.
>1600 yrs
Limited by 200C drift
wall temp. at closure
Fraction Pu,
Am & Cm in
Waste
Fraction Cs & Sr in Waste
225.0
175.0
5.7
5.5
4.4
1.0
1.0
1.0
1.0
10.3
10.5
10.0
44.0
91.0
94.0
54.0
The calculated increase in repository capacity as a function of reduced Cs, Sr, Pu, Am and Cm content with separation after 25 years
Separations and Transmutation Criteria..., Wigeland, et al., Nuc. Tech., 2006
7
Transmutation Benets of Older Fuel
Closed Nuclear Fuel Cycle, Collins, et al., Atalante 2008 Int. Conf., 2008

242
Cm
162.8 d
238
Pu
87.7y
242m
Am
141 y
243
Cm
29.1 y
239
Pu
2.41x10
4
y
244
Cm
18.10 y
240
Pu
6563 y
241
Pu
14.36

y
241
Am
432.2

y
242
Am
16.02

h
243
Am
7370

y
244m
Am
26

m
244
Am
10.1 h
242
Pu
3.733x10
5
y
243
Pu
4.956

h
244
Pu
8.08x10
7
y
75.5%
(n,)
(n,f)
24.5%
92.6%
(n,)
(n,f)
7.4%
26%
(n,)
(n,f)
74%
90%
(n,)
(n,f)
1.0%
9%
(n,)
(>83%)

84%
(n,f)
FPs
16%
(n,)
36.3%
(n,)
(n,f)
66.7%
98.7%
(n,)
(n,f)
1.3%
34%
(n,)
(n,f)
66%
99.2%
(n,)
(n,f)
0.8%
20%
(n,)
(n,f)
80%
99.8%
(n,)
(n,f)
0.25%

(n,)
13%
(n,)
(n,f)
87%
95.3%
(n,)
(n,f)
4.7%
35
33000 MWd/MTIHM
55000 MWd/MTIHM 30
25
20
15
10
5
0
0 20 40 60 80 100
C
m
%

i
n

A
m
-
C
m

F
r
a
c
t
i
o
n
Years after Removal from Reactor
Property measurements on ssion
products and/or their surrogates, glasses,
containment components and geological
materials associated with long-term
isolation in repositories are also of
paramount importance. The properties
of interest include but are not limited
to the thermal conductivity, thermal
diffusivity, specic heat, transformation
energetics, thermal expansion, bulk
density, solidus/liquidus temperatures
and O/M ratio. Clearly, measurement
A G E D F U E L Y O U N G F U E L
241
Am
242
Am
238
Pu
239
Pu
242
Pu
242
Cm
242
Pu
244m
Am
243
Am
244
Cm
241
Pu
17%
83%
of these properties on the materials
mentioned above will necessarily be
carried out in glovebox and hot cell
environments as well as in cold facilities.

Over the past few years NETZSCH-
Gertebau GmbH has become the
leading supplier of thermal analysis
and thermophysical properties
instrumentation to the nuclear industry.
This is because our instruments are
reliable, robust, accurate and easy to
use. All of these attributes are necessary
for instruments operating in harsh
environments such as gloveboxes and
hot cells. Further, the modular design
of our instruments makes them ideally
suited for incorporation into these
environments. Finally, the costs of
operating in hot cells and gloveboxes
are extremely high, making downtime
critical. Our exemplary global service
is therefore one more reason for our
success.
8
Thermophysical Properties
Thermal Conductivity
The thermal conductivity is perhaps the
single most important thermophysical
property and is paramount to the design
of any system operating at elevated or
sub-ambient temperatures. It consists of
a lattice and/or electronic component,
depending on the material (other
components are also possible). It is well
known in the nuclear industry that the
thermal conductivity controls:
temperature gradients in fuel
efciency of cladding and heat
exchangers
Classication of some thermophysical properties
Introduction
Thermophysical properties can be
divided into two categories transport
and thermodynamic. Transport
properties include, but are not limited
to, thermal conductivity, electrical
resistivity and thermal diffusivity.
(Actually, thermal diffusivity is a hybrid
transport/thermodynamic property.)
Thermophysical
Properties
Thermal
Diffusivity
Thermal Expansion
(bulk density)
Thermal
Conductivity
Specic Heat
and Enthalpy
Electrical
Resistivity
Thermodynamic
Properties
Transport
Properties
Thermodynamic properties include
specic heat, transition energetics and
thermal expansion (bulk density).
ability of geological repositories and
container material to dissipate heat
heat transfer in multi-layer fuel
systems, e.g. TRISO.
The complete list is quite long. The
thermal conductivity is greatly affected by
corrosion, hydriding, fouling, O/M ratio,
ssion product carry-over, irradiation
damage, composition, porosity, etc. The
thermal conductivity/thermal diffusivity
of almost all nuclear materials is most
efciently measured by the laser ash
technique (LFA). LFAs can readily be
incorporated into gloveboxes and hot
cells with the appropriate modications.

Specic Heat and Transition
Energetics
The capacity of a material to store
energy is governed, in part, by the
specic heat (sensible heat). It is made
up of lattice, electronic and defect
components, depending on the material.
This property is required for design of
any transient heat transfer process. It is
also used to quantify surface oxidation/
reduction and O/M ratio (defects) of
fuels during processing. In some cases,
the specic heat can be used as an
indicator of the extent of damage in
post irradiation examination (PIE), e.g.
9
stored energy. It is also required to
calculate the thermal conductivity from
thermal diffusivity data.
Transition energetics (latent heat) are
required to characterize solid-solid
transitions, melting/solidication and
decomposition. Both specic heat and
transition energetics are most accurately
and efciently measured by differential
scanning calorimetry (DSC). The specic
heat can also be measured by the laser
ash technique, albeit with reduced
accuracy and only with a reduced number
of data points. (With DSC, generation of
a quasi-continuous set of temperature-
dependent specic heat data is standard.)
With the required expertise, DSCs can
readily be adapted for hot work.


Solidus and Liquidus Temperatures
Solidus and liquidus temperature as
well as melting temperature data are
necessary to establish safe reactor
operating conditions and to model
accident scenarios such as loss of
coolant. These temperatures are
greatly affected by impurities, radiation
damage, O/M ratios, burnup and,
of course, composition. Surprisingly,
solidus/liquidus temperatures are
notoriously difcult to measure
accurately. DSC is the technique
most often employed for these
measurements, but care must be
taken to avoid undercooling during
solidication (especially critical for
metal alloys). Sample time constants
and temperature ramp rates must be
carefully considered. Solidus/liquidus
temperatures of most metal alloys can
also be measured by the laser ash
technique (by utilization of thermal
conductivity/thermal diffusivity data) and
dilatometry can be used for conductors
and insulators alike. For materials that
melt at ultra-high temperatures, thermal
arrest is sometimes employed using
optical pyrometers for the temperature
measurement. All things considered,
DSC is the most versatile and accurate
method.


Thermal Expansion
Thermal expansion can be made up
of lattice, electronic, magnetic and
vacancy/interstitial components,
depending upon the material and
temperature. Thermal expansion
data are key to both reactor and fuel
design. For example, it is necessary for
quantication of:
fuel swelling during irradiation
fuel/coating compatibility (e.g. UO
2
/
graphite/SiC or ZrC)
abrasion and corrosion coating/
substrate compatibility
densication during sintering
thermal expansion coefcients
volume change during melting/
solidication
bulk density
and, as stated earlier, the data can be
used to determine solidus and liquidus
temperatures. By far the most versatile,
accurate and economical technique to
measure thermal expansion is pushrod
dilatometry. Dilatometers are well
suited for glovebox/hot cell work.

Mass Change and Evolved Gases
Temperature-dependent mass change
coupled with evolved gas analysis
provides valuable information to help
quantify: O/M ratio, out-gassing during
fuel processing, corrosion, reduction,
volatile ssion products/actinides
during vitrication, impurities
remaining from the separation process,
etc. A thermogravimetric analyzer
(TGA) or simultaneous TGA-DSC (STA)
instrument coupled to a quadrupole
mass spectrometer (QMS), either
directly or by a heated transfer line,
or a TGA or STA coupled to an FT-IR
via a heated transfer line are widely
employed for these types of analysis.
As with the other techniques previously
discussed, these instruments can easily
be modied for hot work.
10
Instrumentation
Flash Technique
The ash method is the fastest and most
accurate way of measuring the thermal
diffusivity ( thermal conductivity). It
has been estimated that 80-85% of all
thermal diffusivity/thermal conductivity
measurements are carried out using this
technique. This is because of:
easy sample preparation:
coin-sized disk or square/rectangle
(can be even smaller)
exibility: measurements on solids,
liquids, pastes, powder and laminate
samples
small sample size: ideal for
fuels/irradiated materials
fast measurement times: due to
small sample size
high accuracy: usually better than 5%
wide thermal diffusivity/thermal
conductivity range: approx.
0.01 to 1000 W/mK
wide temperature range:
-125C to 2800C
Comparison of the ash method with other techniques utilized in NETZSCH instruments as well as
approximate room temperature thermal conductivity ranges of several types of materials.
Flash (-125C to 2800C)
Hot Wire (RT to 1500C)
Guarded Hot Plate (-160C to 250C)
Heat Flow Meter (-30C to 100C)
0.001 0.010 0.100 1.00 10 100 1000
Thermal Conductivity at RT [W/(m
.
K)]
V
a
c
u
u
m

I
n
s
u
l
a
t
i
o
n
A
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r
,

M
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p
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,

P
U

F
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F
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,

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,
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,

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l
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o
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,

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,

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,

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,

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r
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d
11
1.0
0.5
T

/

T
m
a
x

o
r

V

/

V
m
a
x
As shown below, the front surface of a
sample is heated by a short energy pulse
(xenon or laser) and the time-dependent
temperature rise on the rear surface is
measured by an IR detector. From a plot
of T / T
max
(or V / V
max
) vs half-time, the
thermal diffusivity of a perfectly insulated
sample at one half-time is given by:
a = 0.1388 l
2
/t

where
a = thermal diffusivity (mm
2
/s)
l = sample thickness (mm)
t

= half-time (s)
There are several sophisticated models
to correct for heat loss (non-adiabatic
conditions) and the nite pulse width of
the energy source.
Flash technique
heating
element
protective
tube
sample
thermo-
couple
sample
furnace
power
source
detector

Using the measured thermal diffusivity
values, the thermal conductivity is
calculated by:
(T) = a(T) c
p
(T) (T)
where
= thermal conductivity (W/mK)
= bulk density (g/m
3
)
C
p
= specic heat (J/gK)
Experimental data
1.0 half-time
The bulk density can be obtained from
thermal expansion data, and the specic
heat by either the LFA or a DSC.
12
LFA 467 HyperFlash
The LFA 467 HyperFlash is a Xenon
ash-based system with a compact
design. It covers the temperature range
from -100C to 500C. A variety of
cooling options allow for measure ments
to be carried out across the full
temperature range of the instrument
without having to change either the
furnace or the detector. The integrated
automatic sample changer allows for
unattended analyses on up to
16 samples.
The very high sampling rate and the
unmatched ZoomOptics make for a broad
application range, even for thin samples.

LFA 457 MicroFlash

The LFA 457 embodies the latest

technology for modern laser ash
systems. This bench-top instrument
has a temperature range of -125C to
1100C using two user-exchangeable
furnaces. The vacuum-tight design
enables tests under well-dened
atmospheres. Sample sizes of up to
25.4 mm can be accommodated and
the integrated sample changer allows
simultaneous measurement of up to
3 samples. The innovative infrared
sensor technology employed in the
system enables measurement of the
sample temperature increase, even at
temperatures of -125C.
The vertical arrangement of the sample
holder, furnace and detector simplies
sample placement and, at the same
time, guarantees an optimum signal-to-
noise ratio for the detector signal. The
small footprint of this instrument makes
it ideal for modication for glovebox
and hot cell applications.
Instrumentation
Light/Laser Flash Analysis
LFA 457 modied for
glovebox operation
13
LFA 427
The 427 is the most powerful and
versatile LFA system for research and
development as well as all applications
involving the characterization of
standard and nuclear materials.
The LFA 427 guarantees high precision
and reproducibility, short measurement
times and dened atmospheres over
a temperature range of -120C to
2800C. Special holders for liquid, ber,
paste, powder and laminate samples are
available. Even fuel fragments can be
tested.

The system is vacuum tight to 10
-5
mbar.
The variable laser power and pulse
width functions make it easy to optimize
test parameters.
The NETZSCH LFAs cover almost the entire range of temperatures and materials
of interest to the nuclear industry. For convenience, some of the specications are
summarized in the table below.
Model Temperature Range Atmosphere Energy Detector
LFA 467 -100C to 500C inert, oxid. Xenon ash InSb
LFA 457 -125C to 1100C inert, oxid., red., vac., corr. Laser InSb / MCT
LFA 427 -120C to 2800C inert, oxid., red., vac., corr. Laser InSb / MCT
LFA 427 modied for
hot cell operation
14
Time [s]
Time [s]

T

=

T
R

-

T
S
Difference (from 0)
~ Mass c
p
Difference
~ Mass c
p
T
C

V
o
l
t
a
g
e

[

V
]
(
~

T
e
m
p
e
r
a
t
u
r
e
)
Reference signal
Sample signal
Transition temperature
Area A
~ Transition enthalpy
t
1
t
1
t
2
t
2
T
R
T
S
T
M
T
M
Heat ux DSCs function by measuring
the temperature difference (voltage
difference) between a sample and a
reference while being heated or cooled
at a constant rate. The resulting signal
is proportional to the mass specic
heat (sensible heat) plus the energy
associated with any phase change, etc.
(latent heat). This signal is converted to
actual physical quantities through
calibration using melting point
standards having well-dened heats
of fusion or specic heat standards
with well-established and reproducible
temperature-dependent specic heat
values. This is typically referred to as a
sensitivity calibration. The signal
generated by a heat ux DSC is shown
here.
The temperature-dependent specic
heat is obtained by running a baseline
(empty crucibles), standard and sample
scan. Using these data the specic
heat is calculated by the so-called ratio
method where the specic heat of the
sample is given by:
C
p,s
= C
p,std
Instrumentation
Differential Scanning Calorimetry (DSC)
where
C
p,s
= sample specic heat [J/(gK)]
C
p,std
= standard specic heat [J/(gK)]
m
s
= sample mass [g]
m
std
= standard mass [g]
V
s
= sample scan signal
V
std
= standard scan signal
V
BL
= baseline scan signal
The resulting specic heat curve will also
include any latent heat due to phase
transitions, etc. In the temperature
m
std
V
s
-V
BL
m
s
V
std
-V
BL
region of a phase transition the result is
typically referred to as apparent specic
heat. The resulting peak in the specic
heat curve can then be integrated to
give the transition energy, h (J/g).
Finally, the onset and end of the latent
heat peaks can be used to dene the
solidus and liquidus temperatures as
long as time constants and undercooling
are given proper consideration.
Signal generation in
a heat ux DSC
The NETZSCH F Series DSCs cover most applications of interest to the nuclear
industry. An overview of some of the specications is given in this table.
Model Temperature Range Atmosphere Vacuum Sensor Types
DSC 404 F1 -150C to 2000C inert, oxid., red., vac., corr., humid 10
-4
mbar E, K, S, B, W-Re
DSC 404 F3 -150C to 2000C inert, oxid., red., vac., corr., humid 10
-2
mbar E, K, S, B, W-Re
15
NETZSCH DSC 404 F Pegasus

Series
The F Series DSCs (F1 and F3) have
a temperature range of -150C to
2000C and are vacuum tight down
to 10
-4
mbar. Eight different furnaces
are available and, when equipped
with a double hoist, 2 furnaces can be
mounted simultaneously. There are 13
different user-exchangeable fast-x
plug-in sensors which allow optimization
of sensitivity and time constants.
The F Series was designed specically
for high-temperature specic heat
measurements. Accuracies in the range
of 2.5% can be obtained for most
materials over the temperature range of
-150C to 1400C for specic heat and
better than 2.0% for latent heat over
the temperature range of -150C to
1650C.
Evolved gases can also be identied and
quantied (with optional PulseTA

unit)
by coupling the DSC to an MS, GC-MS
and/or an FT-IR via a heated furnace
adapter head and heated transfer line.
Special options for corrosive gases are
also available.
Automatic sample changers are
available for the F Series, but are not
generally recommended for glovebox/
hot cell operation.
DSC 404 F1 Pegasus

with automatic sample changer

These units are widely used in the
nuclear industry in both cold and hot
applications. The glovebox/hot cell
versions are equipped with special
sample loading mechanisms and sample
carrier adjustment systems to facilitate
operation. These special congurations
have reduced footprints with separate
electronics and MFCs located outside
the glovebox or hot cell.
16
16
Four modified DIL 402 C dilatometers
operating in a hot cell
Rolf, this is an extremely powerful
picture, but it needs some editing.
We have permission to use it.
The volumetric expansion for an
isotropic material is then calculated by:

3T
where
V = volume (cm
3
)
V
0
= initial volume (cm
3
)
Thus, the instantaneous temperature-
dependent bulk density, , for an
isotropic material can be calculated
using:
=
where
m = instantaneous mass (g).
Pushrod dilatometers measure, via
an LVDT, the thermal expansion of a
sample while it is being heated at a
constant rate or held isothermally (with
the exception of non-linear rates in
rate-controlled sintering studies). The
voltage signal is proportional to the
expansion of the sample. This raw signal
is converted to the length change by
calibrating the instrument using a
standard with a well-dened and
reproducible thermal expansion.
The temperature-dependent length
change is used to calculate the
coefcient of linear expansion, , i.e.:
= =
where
L = length (mm)
L
0
= initial length (mm)
T = temperature (C)
Dilatometry (DIL)
Instrumentation
1 L 1 (L
2
-L
1
)
L
0
T L
0
(T
2
-T
1
)
V
V
0

m
V
m
V
0
(1+ 3T)
Four modied DIL 402 C
dilatometers
operating in a hot cell
17
Model Temperature Range Atmosphere l Resolution Type
DIL 402 PC RT to 1600C inert, oxid. 8 nm single pushrod
DIL 402 C -180C to 2000C inert, oxid., red., vac., corr., humid 0.125 / 1.25 nm single pushrod
DIL 402 E -180C to 2800C inert, oxid., red., vac., corr., humid 1.25 nm single pushrod
DIL 402 CD -180C to 2000C inert, oxid., red., vac., corr., humid 0.125 / 1.25 nm dual sample/differential
DIL 402 ED -260C to 30C inert, oxid., red., vac., corr., humid 0.125 / 1.25 nm dual sample/differential
NETZSCH manufactures 5 unique
horizontal dilatometer models which
operate over a temperature range of
-260C to 2800C. The LVDT housings
are thermostatted and have Invar
LVDT mounting systems. This ensures
that the length signal is not disturbed
by the furnace or uctuations in the
room, glovebox or hot cell temperature.
All of these dilatometers (except the
ED) can be equipped with at least 2
user-exchangeable furnaces and
some up to 4. All models except the
PC are vacuum-tight down to 10
-4
mbar
or better. The accuracy is better than
1% for most materials. Graphite, Al
2
O
3

and fused silica sample carriers and
pushrods with sample thermocouple
types E, S, B and W-Re are available.
Special holders for liquid metals, pastes,
powders, bers and thin lms are also
available.
Software options such as c-DTA

,
RCS, density and thermokinetics
allow calculation of phase
transitions, measurement of
densication under variable heating
rate conditions, calculation of bulk
density from linear expansion data
for isotropic samples and kinetic
evaluation during phase transitions
NETZSCH DIL 402 Series
The NETZSCH dilatometers cover almost all conceivable nuclear applications.
For convenience, some of the specications are summarized in this table.
and sintering, respectively. Using
special sample holders, the solidus
and liquidus temperatures can also be
determined.

The small footprint and horizontal
design of the NETZSCH dilatometers
make them ideal for incorporation into
gloveboxes/hot cells.
Dilatometer model 402 C
18
Thermomechanical Analysis (TMA)
determines dimensional changes of
solids, liquids or pasty materials as a
function of temperature and/or time
under a dened mechanical force (DIN
51 005, ASTM E831, ASTM D696,
ASTM D3386, ISO 11359 Parts 1 to
3). It is closely related to Dilatometry,
which determines the length change of
samples under negligible load (DIN
51 045).
Irrespective of the selected type of
deformation (expansion, compression,
penetration, tension or bending), every
change of length in the sample is
communicated to a highly sensitive
Thermomechanical Analysis (TMA)
Instrumentation
inductive displacement transducer
(LVDT) via a push rod and transformed
into a digital signal.
The force imparted to the sample is
generated electromagnetically. This
guarantees a quick response time for
experiments with a changing load,
e.g. tests on creep behavior. A highly
sensitive force sensor (digital resolution
< 0.01 mN) continuously measures
the force exerted via the push rod and
readjusts it automatically. The force
can be applied as a single pulse or as
continuous modulation at frequencies
up to 1 Hz. The force and displacement
signals are measured simultaneously.
Thermomechanical Analysis (TMA)
Standard TMA 402 F1 Hyperion

with double furnace hoist
furnace
sample
push rod
sample carrier
height setting
displacement
transducer
actuator
(static or
modulating)
force sensor
F
19
The NETZSCH TMA is a vertical system
and is available as the F1 or F3.
Both models are vacuum tight with
thermostatted LVDT housings and
Invar mounting systems, making them
ideal for the measurement of low CTE
materials because the measurement
signal is not disturbed by uctuations
in the room, glovebox or hot cell
temperature. Both the F1 and F3 are
available with a double furnace hoist
which allows two furnaces to be
mounted simultaneously (the -150C
to 1000C steel furnace and the RT to
1550C SiC furnace). These furnaces
are interchangeable with the NETZSCH
STA 449 and DSC 404 F Series.
Integrated software-controlled MFCs
mean that sample purge gases can be
switched or mixed (to control e.g. P
O
2
)
as many times as necessary during the
measurement.
Sample holders for expansion,
penetration, tension and 3-point
bending are available in Al
2
O
3
or fused
silica and are easily exchangeable.
Further sample containers for
powders, liquids, pastes and molten
metals are available in several different
materials.
The vertical design of the TMA 402
makes it ideal for coupling to an MS,
GC-MS and/or FT-IR (chimney effect)
and for glovebox/hot cell operation
after, of course, the appropriate
modications such as separation of
electronics, MFCs, etc.
As with the dilatometers, software
options for c-DTA

, RCS, density
The NETZSCH TMAs are suitable for most nuclear applications.
For convenience, some specications are shown here.
Technical Data TMA 402 F1 TMA 402 F3
Max. sample length 30 mm 30 mm
Temperature range -150C to 1550C (2 furnaces)
Atmosphere inert, oxid., red., vac., corr., humid
Measuring range 2.5 mm 2.5 mm
Dig. resolution (length) 0.125 nm 0.125 nm
Force range
0.001 N to 3 N in steps of 0.2 mN
(tension or pressure)
Dig. resolution (force) < 0.01 mN < 0.01 mN
Modulated force Up to 1 Hz -
Final vacuum < 10
-4
mbar < 10
-2
mbar
Gas connections
Protective gas,
2 purge gases
Protective gas,
2 purge gases
Mass ow controller (MFC) Standard Optional
and thermokinetics allow calculation
of phase transitions, densication,
calculation of bulk density, etc.
Further, determination of visco-elastic
properties from measurements using
variable force is possible.
NETZSCH TMA 402 F Hyperion

Series
20
exo
T
1 T
2
T
3
m
1
m
2
m

m

(
%
)
m
W

m
/
t

(
%
/
m
i
n
)
Temperature
DSC
TG
DTG
Instrumentation
Thermogravimetric Analysis (TGA)/Evolved Gas Analysis (EGA)
TGAs measure the mass change of a
sample during heating/cooling or in
an isothermal phase via a sensitive
microbalance. In systems in which the
balance is located on top, the sample
crucible is suspended in the furnace by
a wire or rod. Instruments with such an
arrangement are generally referred to as
hang-down systems. If the balance is
located below the furnace, the sample
crucible sits on a sensor at the terminal
end of a ceramic rod. These systems are
commonly referred to as top-loading.
Some instruments make use of a
horizontal design.
When TGA is coupled with DSC,
simultaneous measurement of mass
change and energetics (simultaneous
thermal analysis STA) with one
instrument is possible. The advantage
of this is that both the mass change
and energetics are measured simulta-
neously on one sample so that the test
conditions, e.g. gas ow rate, gas partial
pressure, heating rate, temperature, etc.
are identical. The rate of mass change is
calculated from the mass signal.
If the STA is coupled to a QMS, GC-MS
and/or an FT-IR, the mass change,
energetics and evolved gases are
measured simultaneously. Of course,
this is ideal because the TGA and DSC
tell us how much, while the evolved
gases tell us what and, generally, why.
STAs can also be run in the so-called
rate controlled mass change mode. In
this case, the sample is not heated at
a constant rate, but in such a fashion
as to produce a constant rate of mass
change. This is ideal for cases where
high rates of mass loss can cause sample
damage and/or skew the results, e.g.,
binder burnout during sintering of
technical ceramics or powder metals.
Measured and calculated STA curves
STA 449 F1 Jupiter

coupled to a 300 amu

QMS 403 D Aolos

prepared for glovebox

21
The NETZSCH STA/EGA systems handle almost all nuclear applications.
For convenience, some system specications are summarized below.
Model Temperature Range Atmosphere Digital Resolution
STA 449 F1 -150C to 2400C inert, oxid., red., vac., corr., humid 0.025 g
STA 449 F3 -150C to 2400C inert, oxid., red., vac., corr., humid 1.0 g
STA 409 CD -150C to 2400C inert, oxid., red., vac., corr., humid < 2.0 g
NETZSCH STA/EGA Systems
NETZSCH produces 3 different STA
systems which cover a temperature
range of -150C to 2400C. There are
9 unique furnaces available and 16
different user-exchangeable fast-x
plug-in sensors which allow sensitivity/
time constant optimization. The
balances are all top-loading and purge
gases ow from the bottom and exit
at the top of the furnace along with
the evolved gases. This arrangement
is ideal for EGA work (chimney effect).
The balances have high capacities and
digital resolutions (see below). The units
are all vacuum tight, making them well
suited for work requiring controlled
atmospheres. The STAs have excellent
long-term stability (low drift) because
the balance chambers are thermostatted
to isolate the balance from uctuations
in glovebox/hot cell temperatures. The
vacuum-tight design and long-term
stability make the NETZSCH STAs
ideal for corrosion and O/M studies.
An optional water vapor furnace and
generation system is an additional
advantage for corrosion studies.
The NETZSCH STAs can be coupled to
EGA systems (e.g., MS, GC-MS, FT-IR)
via a heated adaptor head and heated
transfer line or, in the case of the MS,
directly via SKIMMER

technology.
A well-dened quantity of gas can be
injected into the STA via a PulseTA

unit. This permits calibration of the EGA
system so that the gases released from
the sample can not only be identied,
but quantied as well.
22
The STA 409 CD can be directly coupled
to an MS via SKIMMER

technology
which utilizes a unique supersonic jet
gas transfer system. The SKIMMER

coupling yields the shortest possible
path for the gas transfer from the
sample to the MS. An intense, highly
parallel molecular beam is collimated by
the aerodynamic beam SKIMMER

from
Standard STA 409 CD SKIMMER

the barrel-shaped jet expansion behind

the divergent nozzle. The pressure
reduction of the purge gas ow at
atmospheric pressure down to the high
vacuum behind the SKIMMER

orice is
achieved in two steps along a distance
of less than 20 mm. All components
are heated to at least the sample
temperature and therefore there is little
chance for condensation; even metal
vapors are detected by this unrivaled
coupling system.
The nozzle and SKIMMER

are precisely
machined from either alumina or
amorphous carbon (glassy carbon),
allowing application temperatures of
1450C or 2000C in the corresponding
furnaces. The molecular beams are
analyzed by a quadrupole mass
spectrometer up to high mass numbers
of 512 amu or optionally 1024 amu.
NETZSCH STA/EGA Systems
Instrumentation
23
Standard STA 449 F1 Jupiter

coupled with the

GC-MS via the heated transfer line
Gas chromatography (GC) is a method
for separation of volatile and
semi-volatile compounds with high
resolution. Gas mixtures are separated
based on the differences in component
distribution between a stationary phase
(e.g., inner coating of a capillary) and
a mobile phase (purge gas, e.g., He, N,
Ar, H
2
).
Gas components with low afnity
for the stationary phase but higher
afnity for the mobile phase will be
rapidly carried away by the purge gas,
whereas gases with a high afnity for
the stationary phase will follow with a
relatively signicant time delay
(retention time).
The mobile phase in GC is a gas,
therefore all analytes must be
evaporated and introduced into the
column in gas form.
The stationary phase in the GC is
for universal applications. In current
technology, this is usually a polymeric
coating inside a long and narrow fused
silica capillary.
MS is applied as a detection system at
the outlet of the GC separation column
and will register the time distribution
of the separated gas components in
the purge gas ow. This pre-separation
of gases by the GC, along with the
sensitivity and resolution of the MS,
Some of the GC-MS specications are summarized below.
Technical Data
Mode/Ionization Non-coated inert source, electron impact ionization (EI)
Transfer line temperature 100C to 300C
Furnace adapter
head temperature
max. 300C
Mass lter Monolithic hyperbolic quadrupole
Mass range 1.6 amu to 1050 amu
Mass resolution Unit mass, adjustable
Valve box Heatable up to 300C, Sampling loop 250 l
provide detailed structural information
on most compounds and thus allow for
their precise identication.
The GC-MS can be coupled to any of the
NETZSCH STAs via a heated transfer line.
24
Applications
Thermal Conductivity
20
25
30
35
40
0
5
10
15
20
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
0 400 800 1200 1600 2000 2400 2800
Thermal Conductivity of
some Oxide Ceramics
Al O , 98% TD
2 3
UO , 95% TD, O/M=2.0, 0% BU
2
(U Pu )O , 95% TD, O/M=2.0, 0% BU
95 5 2
ThO , 98% TD
2
Temperature/ C
15
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
30
Temperature/ C
25
0
10
20
1250 0 1000 750 500 250 1500
5
Thermal Conductivity of
some Actinide Nitrides
corrected to 100% TD
NpN
UN
AmN
PuN
Moore, et al., J. Amer. Ceram. Soc., 1970
Arai, et al., 10th IEMPT, 2008
Shown in Figure 14 is the thermal
conductivity of a few actinide
nitrides. Increasing thermal
conductivity with temperature
indicates a significant electronic
component and decreasing
electrical resistivity. Decreasing
thermal conductivity with increasing
ion mass difference suggests
increased phonon-electron
scattering, i.e. shorter mean free
path.
Fig. 13. Thermal Conductivity of some Oxide Ceramics
Fig. 14. Thermal Conductivity of some Nitride Ceramics
Figure 13 depicts the thermal
conductivity of four stoichiometric
oxide ceramics with 95-98%
theoretical density. The materials
show the classical trends for non
(or low) electrical conductors. That
is, exponential and 1/T decay with
increasing temperature due to
defect and phonon-phonon
scattering, respectively. Further,
decreasing thermal conductivity
with increasing difference in ion
mass is typical, that is:
l < l < l < l .
UO ThO Al O BeO 2 2 2 3
Applications
Thermal Conductivity
20
25
30
35
40
0
5
10
15
20
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
0 400 800 1200 1600 2000 2400 2800
Thermal Conductivity of
some Oxide Ceramics
Al O , 98% TD
2 3
UO , 95% TD, O/M=2.0, 0% BU
2
(U Pu )O , 95% TD, O/M=2.0, 0% BU
95 5 2
ThO , 98% TD
2
Temperature/ C
15
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
30
Temperature/ C
25
0
10
20
1250 0 1000 750 500 250 1500
5
Thermal Conductivity of
some Actinide Nitrides
corrected to 100% TD
NpN
UN
AmN
PuN
Moore, et al., J. Amer. Ceram. Soc., 1970
Arai, et al., 10th IEMPT, 2008
Shown in Figure 14 is the thermal
conductivity of a few actinide
nitrides. Increasing thermal
conductivity with temperature
indicates a significant electronic
component and decreasing
electrical resistivity. Decreasing
thermal conductivity with increasing
ion mass difference suggests
increased phonon-electron
scattering, i.e. shorter mean free
path.
Fig. 13. Thermal Conductivity of some Oxide Ceramics
Fig. 14. Thermal Conductivity of some Nitride Ceramics
Figure 13 depicts the thermal
conductivity of four stoichiometric
oxide ceramics with 95-98%
theoretical density. The materials
show the classical trends for non
(or low) electrical conductors. That
is, exponential and 1/T decay with
increasing temperature due to
defect and phonon-phonon
scattering, respectively. Further,
decreasing thermal conductivity
with increasing difference in ion
mass is typical, that is:
l < l < l < l .
UO ThO Al O BeO 2 2 2 3
Applications

Depicted here is the thermal conductivity
of four stoichiometric oxide ceramics
with 95% to 98% theoretical density.
The materials show the classical trends
for non (or low) electrical conductors.
That is, exponential and 1/T decay with
increasing temperature due to defect and
phonon-phonon scattering, respectively.
Further, decreasing thermal conductivity
with increasing difference in ion mass is
typical, that is:

UO
2
<
ThO
2
<
Al
2
O
3
<
BeO
.

Increasing thermal conductivity with
temperature indicates a signicant
electronic component and decreasing
electrical resistivity. Decreasing thermal
conductivity with increasing ion mass
difference suggests increased phonon-
electron scattering, i.e., shorter mean
free path.
Thermal Conductivity
Thermal Conductivity of Four Stoichiometric Oxide Ceramics
Thermal Conductivity of Some Actinide Nitrides
25
Shown in Figure 15 is the thermal
conductivity of UN separated into
the lattice and electronic
components. Here the typical lattice
1/T and increasing electronic
behavior is displayed. Note the non-
coincidental agreement between
the lattice thermal conductivities of
UN and UO2. It must be pointed out
here that the lattice and electronic
components of thermal conductivity
were calculated from thermal
conductivity and electrical resistivity
measurements using a fitting
routine. The Wiedemann-Franz-
Lorenz (WFL) law, which can lead
to significant errors in regions of
non-elastic scattering, was not
applied directly.
21
9
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
18
Temperature/ C
3
6
12
15
Thermal Conductivity of
Uranium Nitride
Electronic Contribution
Lattice Contribution
Total
UO - Lattice
2
0 1000 750 500 250
21
Moore, et al.,
J. Amer. Ceram. Soc., 1970
Figure 16 shows the thermal
conductivity of three carbide
ceramics. Even though a conductor,
SiC follows the classical lattice
thermal conductivity trend, while
ZrC displays more of a dominant
electronic trend. UC shows only a
slight decrease in thermal
conductivity with increasing
temperature. This is due to the fact
that the electronic and lattice
component trends almost nullify
each other even though the
electronic component is dominant.
2000 0
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
120
1600 1200 800 400
Temperature/ C
80
0
Thermal Conductivity of
some Carbide Ceramics
ZrC SiC UC
100
40
60
20
Shown in Figure 15 is the thermal
conductivity of UN separated into
the lattice and electronic
components. Here the typical lattice
1/T and increasing electronic
behavior is displayed. Note the non-
coincidental agreement between
the lattice thermal conductivities of
UN and UO2. It must be pointed out
here that the lattice and electronic
components of thermal conductivity
were calculated from thermal
conductivity and electrical resistivity
measurements using a fitting
routine. The Wiedemann-Franz-
Lorenz (WFL) law, which can lead
to significant errors in regions of
non-elastic scattering, was not
applied directly.
21
9
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
18
Temperature/ C
3
6
12
15
Thermal Conductivity of
Uranium Nitride
Electronic Contribution
Lattice Contribution
Total
UO - Lattice
2
0 1000 750 500 250
21
Moore, et al.,
J. Amer. Ceram. Soc., 1970
Figure 16 shows the thermal
conductivity of three carbide
ceramics. Even though a conductor,
SiC follows the classical lattice
thermal conductivity trend, while
ZrC displays more of a dominant
electronic trend. UC shows only a
slight decrease in thermal
conductivity with increasing
temperature. This is due to the fact
that the electronic and lattice
component trends almost nullify
each other even though the
electronic component is dominant.
2000 0
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/
W
/
(
m

K
)
120
1600 1200 800 400
Temperature/ C
80
0
Thermal Conductivity of
some Carbide Ceramics
ZrC SiC UC
100
40
60
20

Even though a conductor, SiC follows
the classical lattice thermal conductivity
trend, while ZrC displays more of a
dominant electronic trend. UC shows
only a slight decrease in thermal
conductivity with increasing temperature.
This is due to the fact that the electronic
and lattice component trends almost
nullify each other even though the
electronic component is dominant.

In this example, the thermal conductivity
of UN has been separated into the
lattice and electronic components. Here
the typical lattice 1/T and increasing
electronic behavior is displayed. Note the
noncoincidental agreement between the
lattice thermal conductivities of UN and
UO
2
. It must be pointed out here that
Thermal Conductivity of Uranium Nitride
the lattice and electronic components
of thermal conductivity were calculated
from thermal conductivity and electrical
resistivity measurements using a tting
routine. The Wiedemann-Franz-Lorenz
(WFL) law, which can lead to signicant
errors in regions of non-elastic
scattering, was not applied directly.
Thermal Conductivity of Three Carbide Ceramics
26
Temperature/ C
0 1000 600
0.2
0.6
0.8
1.0
1.4
1.2

400 200 800
Specific Heat of
Zr-40wt%U Metallic Fuel
Measured
Calculated using Neumann-Kopp
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
0.4
B. H. Lee, et al.,
J. Nuc. Mat., 2007
Specic Heat of IN-718

The specic heat and heat of fusion
of IN-718 up to 1450C during
heating and cooling are presented
here. Integration of the melting peak
yields H185 J/g 5.0%. The solidus
and liquidus temperatures were also
determined from these data. It should
be noted however that care must be
taken not to lose sight of possible
undercooling, which is not atypical
for metals. The solidus and liquidus
temperatures are 1252C and 1347C,
respectively.
Specic Heat of Zr-40wt%U
Metal Fuel

The specic heat of Zr-40wt%U fuel
was measured between 25C and
1000C. Other than the endothermic
peak between approximately 550C
and 620C, which is due to the phase
transition, the measured specic
heat values are in reasonably good
agreement with those calculated by the
Neumann-Kopp rule.
Specic Heat and Transition Energetics
Applications
27
0.5
0
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
2.0
2000
Temperature/ C
1.0
0.0
400 800 1600 1200 2400
1.5
Gd O 2 3
Dy O 2 3
Eu O 2 3
Linear Thermal Expansion of
some Neutron Absorbers
B C 4
HfB2
ZrB2
0.2
0
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
1.0
800
Temperature/ C
0.4
0.0
200 400 600 1000
0.8
0.6
Linear Thermal Expansion
of some Elemental
Neutron Absorbers
Dy
Er
Cd
B
Hf
Gd
The thermal expansion of high-
purity POCO graphite over the
temperature range of 500 to
2800C is given in Figure 19.
Clearly the reproducibility is
excellent and, as shown, the
deviation from literature values is
significantly less than 1.0%.
23
Figure 20 shows the thermal
expansion of several nitride
ceramics. It is interesting to note
that the thermal expansion
increases with ion mass difference.
This increasing asymmetric
behavior is also responsible for
increased phonon and phonon-
electron scattering, resulting in
shorter mean free paths and
therefore inverse behavior between
thermal expansion and thermal
conductivity in many ceramics.
Thermal Expansion
Temperature/ C
500 1000
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
0.0
1500 2000 2500
0.5
1.0
3.0
1.5
2.0
2.5
3000
Thermal Expansion - Heat (%) 0.7869 1.2472 1.7406 2.2940
Thermal Expansion - Cool (%) - - 1.7535 2.2956
Literature (%) 0.7871 1.2509 1.7536 2.2941
Maximum Deviation (%) (rel.) 0.03 0.30 0.74 0.07
1000C 2 1500C 000C 2500C
Heat
Cool
Literature
2800C, 2.6257%
Thermal Expansion of
POCO Graphite
1
0
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
3
2500 2000 1500 1000 500
Temperature/ C
2
0
Linear Thermal Expansion
of some Nitride Ceramics
AlN
BN
UN
ZrN
AmN
Thermal Expansion of Some Thermal
Neutron Absorbers

The thermal expansion of some ceramic
and elemental neutron absorbers is
presented here. In general, these
materials expand somewhere between
1.0% and 3.0% between 25C and
the melting temperature. This is the
expected behavior.
Thermal Expansion
Thermal Expansion of Some
Nitride Ceramics

In comparing the thermal expansion of
several nitride ceramics, it is interesting
to note that the thermal expansion
increases with ion mass difference. This
increasing asymmetric behavior is also
responsible for increased phonon and
phonon-electron scattering, resulting in
shorter mean free paths and therefore
inverse behavior between thermal
expansion and thermal conductivity in
many ceramics.
28
Urania
24
Presented here is the oxidation of
stoichiometric UO in an air
2
atmosphere. The conversion from
UO to U O to U O is of course
2 3 7 3 8
accompanied by mass increases of
1.14 and 1.72%. The exothermal
energetics of the transitions are
clearly shown by the DSC curve. It
is interesting to note the excellent
correlation between the mass
change, rate of mass change and
energetic curves. This plot clearly
shows the advantage of
simultaneous TG-DSC (STA)
measurements using one
instrument.
Fig. 21. Mass Change of Hyperstoichiometric UO
2
Fig. 22. Oxidation of UO
2
Plotted in Figure 21 are the mass
change and rate of mass change of
hyperstoichiometric UO in inert
2
and reducing atmospheres. Clearly
the curves overlay until 325C.
The first mass loss step below
325C is due to the evolution of
moisture and impurities. Above
325C the curves deviate because
of the greater oxygen loss in the
reducing atmosphere. By 700C the
urania is stoichiometric in the
reducing atmosphere, while in the
inert atmosphere the material
remains over-stoichiometric. This
has far-reaching consequences
with regard to the sinterability.
- 5
- 2
1
-250
-150
-100
Temperature/C
0 400 700 200 600 100 300 500
10
-300
7
4
E
n
e
r
g
e
t
i
c
s
/

V
M
a
s
s

C
h
a
n
g
e
/
%
-200
-0.4
R
a
t
e

o
f

M
a
s
s

C
h
a
n
g
e
/
m
g
/
m
i
n
0.8
0.0
0.4
1.2
1.6
-50
50
100
0
+
+
1
8
9
.
3

C
3
7
1
.
9

C
1.72%
1.14%
UO U307 U308 2
Oxidation of UO2
Mass Change
Energetics
Rate of Mass Change
Temperature/C
-20
-15
0
M
a
s
s

C
h
a
n
g
e
/
%
-5
98.5
100.0
99.0
99.5
0 800 1400 400 1200 1600 200 600 1000
Mass Change and
Rate of Mass Change of UO
2
-10
R
a
t
e

o
f

M
a
s
s

C
h
a
n
g
e
/
(
%
/
m
i
n
)

x

1
0
-
2
Inert
Reducing

- 5
- 2
1
-250
-150
-100
Temperature/ C
0 400 700 200 600 100 300 500
10
-300
7
4
E
n
e
r
g
e
t
i
c
s
/

V
M
a
s
s

C
h
a
n
g
e
/
%
-200
-0.4
R
a
t
e

o
f

M
a
s
s

C
h
a
n
g
e
/
m
g
/
m
i
n
0.8
0.0
0.4
1.2
1.6
-50
50
100
0
+
+
1
8
9
.
3

C
3
7
1
.
9

C
1.72%
1.14%
UO U 0 U 0
2 3 7 3 8
Oxidation of UO2
Mass Change
Energetics
Rate of Mass Change

Plotted are the mass change and rate
of mass change in inert and reducing
atmospheres. Clearly the curves overlay
until 325C. The rst mass loss step
below 325C is due to the evolution of
moisture and impurities. Above 325C
the curves deviate because of the greater
oxygen loss in the reducing atmosphere.
By 700C the urania is stoichiometric in
the reducing atmosphere, while in the
inert atmosphere the material remains
over-stoichiometric. This has far-reaching
consequences with regard to the
sinterability.
Applications

The conversion from UO
2
to U
3
O
7
to
U
3
O
8
is of course accompanied by
mass increases of 1.14% and 1.72%.
The exothermal energetics of the
transitions are clearly shown by the
DSC curve. It is interesting to note
the excellent correlation between the
mass change, rate of mass change
and energetic curves. This plot clearly
shows the advantage of simultaneous
TG-DSC (STA) measurements using one
instrument.
Oxidation of Stoichiometric UO
2
in an Air Atmosphere
Urania
Mass Change of Hyperstoichiometric UO
2
C
o
u
r
t
e
s
y

o
f

S
E
P
M
29
0.30
300
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
0.40
1500
Temperature/ K
0.35
0.25
500 700 900 1100 1300 1700
Matzke, et al.
J. Nuc. Mat., 1997
Specific Heat of
UO at 0% BU 2+x
0.04
0
0.084
0.04
x
Temperature/ K
500 1500 2500
T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y
/
c
m

/
s

0.002
1000 2000 3000
0.004
0.006
0.010
0.016
0.020
0.008
0.012
0.014
0.018
1 ms pulse width
10 ms pulse width
Ronchi, et al.
J. of App. Phy., 1999
Thermal Diffusivity of
95% Dense Stoichiometric UO
2
The specic heat of stoichiometric
and overstoichiometric UO
2
are shown
here. The stoichiometric UO
2
follows
the classical temperature-dependent
specic heat trend, while that for UO
2.04

and UO
2.084
display an endothermic
peak between approximately 600 and
950K. This is due to energy required
to dissolve the U
4
O
9
phase. Notice that
the peak area for UO
2.084
is larger than
that for UO
2.04
because of the greater
quantity of the U
4
O
9
phase.
Specic Heat of UO
2
Thermal Diffusivity of UO
2
The thermal diffusivity of 95% dense
stoichiometric UO
2
follows the expected
1/T behavior for lattice-driven transport
at these temperatures. It should be
noted that the thermal conductivity
does not display this trend at
temperatures above 2000K, because
the specic heat does not follow the
Debye theory.
30
T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y
/
m
m
2
/
s
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Thermal Diffusivity of (U,Ce)O
2-x
Ceria Content (%)
0
20
25
30
Temperature/ C
0 800 1400 400 1200 1600 200 600 1000
Courtesy of A. T. Nelson
Los Alamos National Lab
Private communication
-1
a = A + B T
0 200 400 600 800 1000 1200 1400 1600
Temperature/ C
I
n
v
e
r
s
e

T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y
/
s
/
m
m
2
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Inv. Thermal Diffusivity of (U,Ce)O
2-x
Ceria Content (%): 0 20 25 30
Ceria
Cont. (%)
A
2
(s/mm )
B
2
(s/mm -C)
-4
0 0.2504 8.50 10
20 0.7067 9.20
-4
10
25 1.0373 8.84
-4
10
30 1.5248 8.33
-4
10
Applications
Urania
Thermal Diffusivity of (U,Ce)O
2-X

The thermal diffusivity of (U,Ce)O
2-X

follows the expected 1/T trend for lattice
transport. Also, the impact of increased
lattice strain ( defect-phonon
scattering) with increasing Ce content
on thermal diffusivity is obvious.

Inverse Thermal Diffusivity of
(U,Ce)O
2-X
Here, the inverse thermal diffusivity
a
-1
= A + B
.
T (A and B represent
defect-phonon and phonon-phonon
scattering, respectively) is plotted
against temperature and Ce content.
As anticipated, this yields a series of
curves with a relatively constant slope,
B. The effect of solutionized Ce ions on
defect-phonon scattering can be further
quantied by plotting A against the Ce
content.
31
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
2
Temperature/ C
-2
-8
-6
-4
0
R
a
t
e

o
f

L
e
n
g
t
h

C
h
a
n
g
e
/
%
/
m
i
n
-2.2
-1.4
0.2
-0.2
0.0
-0.6
-2.0
-1.6
-1.0
Linear Thermal Expansion of Gd O 3
during Sintering @ P 1.0 O2
2
20
10
5
2.5
b(K/min) Expansion Rate
1600 0 1200 1000 600 200 400 800 1400
-1.8
-1.2
-0.8
-0.4
Temperature/ C
0 1200 1600 600
0.25
0.35
0.45
0.55
0.75
0.65

1400 1000 400 200 800
0.40
0.50
0.60
0.70
Specific Heat of Gd O 2 3
@ b = 20 K/min and P 1.0
O2
1st Heat (green)
2nd Heat (sintered)
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
0.30
DH 14.6 J/g D
b
Sintering of Gadolinia

Shown here are the densication and
rate of densication of GdO
1.5
. The
densication follows the expected
heating rate and temperature
dependence up to 1250C. At
1250C the heating rate dependence
disappears and the rate of densication
increases dramatically. This is due to the
cubic to monoclinic phase transition,
which signicantly complicates the
interpretation of the sintering data.
Specic Heat of Gadolinia
This plot depicts the specic heat of
GdO
1.5
during the rst (sintering) and
second heatings. Clearly the phase
transition, with a H of 14.6 J/g, is
irreversible. This has been veried by
XRD data. The low temperature
endothermic and exothermic trends in
the rst heating data are due to the
release of moisture and other impurities.
Gadolinia
32
-8
1800 0
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
2
1200 1000 600 200
Temperature/ C
-2
-14
400 800 1400 1600
-12
-10
-6
-4
0
-0.5
-0.4
-0.3
0.0
0.1
-0.1
-0.2
R
a
t
e

o
f

L
e
n
g
t
h

C
h
a
n
g
e
/
%
/
m
i
n
Linear Thermal Expansion of
CeO during Sintering
2
@ P 0.2 O2
20 K/min
10 K/min
5 K/min
2.5 K/min
1 K/min
Expansion Rate
O
/
M

R
a
t
i
o
2.000
1600 1400 1200 1000 200
Temperature/ C
1.975
O/M Ratio of CeO as a Function of 2
Temperature and at 10 K/min PO2
400 600 800
Increasing PO2
1.980
1.985
1.990
1.995
Densication of CeO
2

The shrinkage and rate of shrinkage
of ceria at ve different heating rates
during sintering are plotted here. The
samples were pressed to 51-53%
theoretical density at 355 MPa. No
binders or mold lubricants were
employed. The onset of densication
occurs at 800C and sintering is not
complete by 1660C. Typical heating rate
dependence due to rate-limited metal
atom diffusion is displayed. The curves
show a two-step densication process
which is somewhat atypical. Final density
was 81-85% of theoretical.
O/M Ratio of CeO
2
During Sintering

This gure shows the O/M ratio during
heating. These values were calculated
from TGA data measured under multiple
partial pressures of oxygen (P
O
2
).
Sample preparation was identical to that
above. During heating the O/M starts
to decrease at 1000C and there are
clearly different reduction rates resulting
from the variable P
O
2
over the sample.
The process is reversible. The resulting
deviation from stoichiometry has a
profound effect on the sinterability.
Ceria
Applications
33
Temperature/ C
0 800 1400 400 1200 1800 200 600 1000
0.30
0.40
0.45
0.60
0.70
0.55
0.65

S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
1600
0.35
0.50
Specific Heat of CeO
2
during Sintering @ P 0.2 O2
With Reduction
Without Reduction
Extrapolated
3.0
3.5
4.0
5.5
Temperature/C
0 800 1400 400 1200 1800 200 600 1000 1600
6.0
5.0
4.5
B
u
l
k

D
e
n
s
i
t
y
/
g
/
c
m
3
0.30
0.40
0.45
0.60
0.70
0.55
0.65

S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
0.35
0.50
1.0
0.0
0.2
0.6
0.4
0.8
I
n
v
e
r
s
e

N
o
r
m
a
l
i
z
e
d

O
/
M

0
2
4
8
6
1
3
5
7
T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y
/
(
c
m
2
/
s
)

1
0
-
3
Properties of CeO
during Sintering @ P 0.2 O
2
2
Thermal Diffusivity -
Specific Heat with Reduction
Specific Heat w/o Reduction
Specific Heat Extrapolated
O/M - Heat
3 Sample Avg.
Bulk Density
Rate of Bulk Density Change
O
/
M
=
1
.
9
9
9
5
O
/
M
=
1
.
9
8
9
5
O
/
M
=
1
.
9
8
4
0

Depicted here is the specic heat of
ceria with and without reduction.
Sample preparation remained
unchanged. In the absence of reduction
the specic heat follows the Debye
theory and is in good agreement with
published values. With reduction
the specic heat (actually apparent
specic heat) increases non-linearly
with temperature. This is a result of the
energy required for the increased rate of
defect formation. The reduction becomes
obvious at 950C. The difference
between the two curves is often referred
to as the excess specic heat.
In this gure the thermal diffusivity,
specic heat, bulk density, rate of
change of bulk density and O/M are
superimposed. First, the correlation
between the specic heat and O/M is
obvious. Next, the thermal diffusivity
increases between 400C and
850C due to surface diffusion (no
densication). The increase in thermal
diffusivity above 850C is a result of
decreasing porosity (densication), but
is partially attenuated by the decreasing
O/M (increased defect scattering). The
densication (diffusion) rate between
O/M=1.9995 and 1.9840 (1165C
and 1620C) is controlled, in part,
by the O/M-created defects. Likely
controlling mechanisms are VMMi /
cluster. XRD measurements show that
above 1600C coarsening occurs at
the expense of densication, which
manifests itself as a drop in the
sintering rate.
Specic Heat of CeO
2
During Sintering
Property Evolution of CeO
2
During Sintering
34
Specifc Heat and Transition Energetics
22
The heat flow during heating and
cooling for a Zr-Nb alloy over the
temperature range of 400 to
1050C is presented in Figure 18.
Of interest here is the solid-solid
endothermal phase transition
between 815 and 990C on
heating. Upon cooling, the exo-
thermal phase transition is shifted
to lower temperatures, i.e. between
985 and 750C. Notice that the
transition energetics are relatively
equal at 47.4 and 47.5 J/g on
heating and cooling, respectively.
This is not atypical for metal alloys.
Fig. 18. Heat Flow in a Zirconium Alloy
Depicted in Figure 17 is the specific
heat of graphite over the tempera-
ture range of -100 to 1300C. As
expected, the trend follows the
Debye theory (electronic specific
heat is negligible at these
temperatures). The measured and
published values deviate by a
maximum of 5.0% and are
generally within 2.0%. Note the
reproducibility of the measurements
over both the low-temperature (LT)
and high-temperature (HT) ranges.
Temperature/ C
0 400 800 1200
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
200 600 1000 1400
0.5
2.5
1.0
1.5
2.0
-200
0.0
Sample 1 - Run 1 (LT)
Sample 1 - Run 2 (LT)
Sample 2 - Run 1 (LT)
Sample 2 - Run 2 (LT)
Sample 1 - Run 1 (HT)
Sample 1 - Run 2 (HT)
Sample 2 - Run 1 (HT)
Sample 2 - Run 2 (HT)
Graphite
Temperature/ C
400 800 500 900 600 700
-0.10
-0.05
0.00
0.05
0.10

D
S
C
/
m
W
/
m
g
867.0C
779.3C
889.3C
858.5C
814.2C
1000 1100
948.8C
983.9C
-47.46 J/g
47.37 J/g
+
+
+
+
+ +
+
+
+
+
++
++
Zirconium Alloy
(Zr-Nb-Fe)
Heat
Cool
The thermal expansion of high-
purity POCO graphite over the
temperature range of 500 to
2800C is given in Figure 19.
Clearly the reproducibility is
excellent and, as shown, the
deviation from literature values is
significantly less than 1.0%.
23
Figure 20 shows the thermal
expansion of several nitride
ceramics. It is interesting to note
that the thermal expansion
increases with ion mass difference.
This increasing asymmetric
behavior is also responsible for
increased phonon and phonon-
electron scattering, resulting in
shorter mean free paths and
therefore inverse behavior between
thermal expansion and thermal
conductivity in many ceramics.
Thermal Expansion
Temperature/ C
500 1000
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
0.0
1500 2000 2500
0.5
1.0
3.0
1.5
2.0
2.5
3000
Thermal Expansion - Heat (%) 0.7869 1.2472 1.7406 2.2940
Thermal Expansion - Cool (%) - - 1.7535 2.2956
Literature (%) 0.7871 1.2509 1.7536 2.2941
Maximum Deviation (%) (rel.) 0.03 0.30 0.74 0.07
1000C 2 1500C 000C 2500C
Heat
Cool
Literature
2800C, 2.6257%
Thermal Expansion of
POCO Graphite
1
0
L
i
n
e
a
r

T
h
e
r
m
a
l

E
x
p
a
n
s
i
o
n
/
%
3
2500 2000 1500 1000 500
Temperature/ C
2
0
Linear Thermal Expansion
of some Nitride Ceramics
AlN
BN
UN
ZrN
AmN
Specic Heat of Graphite

The specic heat of graphite was
measured over the temperature range
of -100C to 1300C. As expected,
the trend follows the Debye theory
(electronic specic heat is negligible
at these temperatures). The measured
and published values deviate by a
maximum of 5.0% and are generally
within 2.0%. Note the reproduc-
ibility of the measurements over
both the low-temperature (LT) and
high-temperature (HT) ranges.
Graphite
Applications
Thermal Expansion of POCO
Graphite
The thermal expansion of high-purity
POCO graphite was measured over the
temperature range of 500C to 2800C.
Clearly the reproducibility is excellent
and, as shown, the deviation from
literature values is signicantly less
than 1.0%.
35
Temperature/C
20
40
T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y
/
c
m

/
s
0.0
1.2
0.4
0.8
0 2000 1000 3000 500 1500 2500
80
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/

W
/
(
m
K
)

0.2
0.6
1.0
0
60
100
120
140
Thermal Diffusivity and Thermal Conductivity
of Graphite
Thermal Diffusivity
Thermal Conductivity
Temperature/C
500 0
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
2.00
1.50
0.00
100
0.50
1.00
2.50
150 200 250 400 350 300 50 450
Specific Heat and Stored
Energy in Irradiated
20 2
Graphite @ 510 n/cm
T
=150C
irr
T
=200C
irr
T =250C
irr
Non-irradiated
Temperature/C
20
40
T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y
/
c
m

/
s
0.0
1.2
0.4
0.8
0 2000 1000 3000 500 1500 2500
80
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
/

W
/
(
m
K
)

0.2
0.6
1.0
0
60
100
120
140
Thermal Diffusivity and Thermal Conductivity
of Graphite
Thermal Diffusivity
Thermal Conductivity
Temperature/C
500 0
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
2.00
1.50
0.00
100
0.50
1.00
2.50
150 200 250 400 350 300 50 450
Specific Heat and Stored
Energy in Irradiated
20 2
Graphite @ 510 n/cm
T
=150C
irr
T
=200C
irr
T =250C
irr
Non-irradiated
Stored Energy in Graphite
Here the apparent specic heat curves
for irradiated graphite are superimposed
on those for the true specic heat of
unirradiated graphite. As expected, the
lower irradiation temperature, T
irr
, results
in more stored energy because fewer
defects are annealed out. Of course,
once T
irr
is exceeded stored energy is
released, resulting in a decrease in the
apparent specic heat.
Thermal Diffusivity and Thermal
Conductivity of Graphite
The thermal diffusivity of graphite was
measured over the temperature range
of 25C to about 2800C. The thermal
conductivity was calculated using the
measured specic heat, bulk density and
thermal diffusivity data. The calculated
thermal conductivity follows the
expected 1/T behavior for graphite.
36
Temperature/C
0.0
0.5
2.5
M
a
s
s

C
h
a
n
g
e
/
%
2.0
100
115
105
110
400 700 1000 900 1100 500 600
1.0
I
o
n

C
u
r
r
e
n
t
/
A

1
0
-
9
1.5
800
Oxidation of Zircaloy-4 Cladding
in a Water Vapor Atmosphere
b(K/m) Mass Detected H
2
10
5
Specifc Heat and Transition Energetics
22
The heat flow during heating and
cooling for a Zr-Nb alloy over the
temperature range of 400 to
1050C is presented in Figure 18.
Of interest here is the solid-solid
endothermal phase transition
between 815 and 990C on
heating. Upon cooling, the exo-
thermal phase transition is shifted
to lower temperatures, i.e. between
985 and 750C. Notice that the
transition energetics are relatively
equal at 47.4 and 47.5 J/g on
heating and cooling, respectively.
This is not atypical for metal alloys.
Fig. 18. Heat Flow in a Zirconium Alloy
Depicted in Figure 17 is the specific
heat of graphite over the tempera-
ture range of -100 to 1300C. As
expected, the trend follows the
Debye theory (electronic specific
heat is negligible at these
temperatures). The measured and
published values deviate by a
maximum of 5.0% and are
generally within 2.0%. Note the
reproducibility of the measurements
over both the low-temperature (LT)
and high-temperature (HT) ranges.
Temperature/ C
0 400 800 1200
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
200 600 1000 1400
0.5
2.5
1.0
1.5
2.0
-200
0.0
Sample 1 - Run 1 (LT)
Sample 1 - Run 2 (LT)
Sample 2 - Run 1 (LT)
Sample 2 - Run 2 (LT)
Sample 1 - Run 1 (HT)
Sample 1 - Run 2 (HT)
Sample 2 - Run 1 (HT)
Sample 2 - Run 2 (HT)
Graphite
Temperature/ C
400 800 500 900 600 700
-0.10
-0.05
0.00
0.05
0.10

D
S
C
/
m
W
/
m
g
867.0C
779.3C
889.3C
858.5C
814.2C
1000 1100
948.8C
983.9C
-47.46 J/g
47.37 J/g
+
+
+
+
+ +
+
+
+
+
++
++
Zirconium Alloy
(Zr-Nb-Fe)
Heat
Cool

Presented here are the mass gain and
detected H
2
during oxidation of
Zircaloy-4 cladding in a steam
atmosphere. The oxidation is due, of
course, to the highly exothermic reaction
Zr + 2H
2
O ZrO
2
+ 2H
2
+ H.
The heating rate dependence of the
oxidation and therefore the H
2

production is obvious. At the 5 K/min
heating rate the rate of mass gain and
H
2
production reach steady-state at
approximately 950C, which is not the
case for the faster 10 K/min rate.
Cladding
Oxidation of Zircaloy-4
Heat Flow in a Zirconium Alloy
The heat ow during heating and
cooling in a Zr-Nb alloy over the
temperature range of 400C to
1050C has been analyzed. Of interest
here is the solid-solid endothermal
phase transition between 815C and
990C on heating. Upon cooling, the
exothermal phase transition is shifted
to lower temperatures, i.e. between
985C and 750C. Notice that the
transition energetics are relatively equal
at 47.4 J/g and 47.5 J/g on heating and
cooling, respectively. This is not atypical
for stable metal alloys.
Applications
37
The thermal diffusivity and specific
heat of a waste glass consisting of
oxides ranging from alumina to
neodymia are plotted in Figure 23.
The specific heat data show the
glass transition (endothermal) in the
range of 500C followed by cold
crystallization (exothermal) between
600 and 750C, indicating that the
sample was cooled fast enough to
produce a significant amorphous
phase. Also, the large excess
enthalpy peak superimposed on the
glass transition may indicate
significant aging time below the
transition. The diffusivity displays
the classical 1/T behavior followed
by a significant drop across the
glass transition. The correlation
between the two data sets is
excellent.
25
Fig. 23. Thermal Difusivity and Specifc Heat of a Waste Glass
E. Post paragraph
Fig. 24. Title
Need plot and paragraph from
Dr. Post on TG/MS measurements
done on one of the PNNL surrogate
waste compositions.
Waste Glass
Temperature (C)
0 600 800 200 400
1.00
2.00
S
p
e
c
i
f
i
c

H
e
a
t
/
J
/
(
g

K
)
1.25
0.0025
0.0030
0.0035
0.0040
0.0050
0.0045

T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y
/
c
m

/
s
2
Waste Glass
Specific Heat
Thermal Diffusivity
1.75
1.50
0.75
0.50
50
1400 0
M
a
s
s

C
h
a
n
g
e
/
%
100
1000 600 200
Temperature/C
80
400 800 1200
30
40
60
70
90
-0.5
0.0
0.5
3.0
3.5
2.0
1.5
-
1
0
I
o
n

C
u
r
r
e
n
t
/
A

1
0
1.0
2.5
20
-9.8%
-9.4%
-12.1%
-10.8%
-7.8%
NO
658.1C
CO2
214.7C
159.6C
H O 2
NO2
496.4C

The thermal diffusivity and specic heat
of a waste glass consisting of oxides
ranging from alumina to neodymia are
plotted here. The specic heat data
show the glass transition (endothermal)
in the range of 500C followed by cold
crystallization (exothermal) between
600C and 750C, indicating that the
sample was cooled fast enough to
produce a signicant amorphous phase.
Also, the large excess enthalpy peak
superimposed on the glass transition
may indicate signicant aging time
below the transition. The diffusivity
displays the classical 1/ T behavior
followed by a signicant drop across


Waste material can contain silicates like
clays contaminated with radioactive
inorganic salts (hydrates, sulphates,
nitrates etc.). The processing of these
waste materials is often done by a heat
treatment. TG-MS measurements allow
the determination, identication and
quantication of the evolved gases
during heating of these materials. The
surrogate material for this investigation
contained vermiculite and alkali and
earth alkali nitrates. During linear
heating at 10 K/min in a He atmosphere,
water, nitrogen oxide, nitrogen dioxide
and carbon dioxide were detected.
The water came off between RT
and about 400C, nitrogen dioxide
shows two intensity maxima at about
180C and 497C. The nitrogen oxide
emission starts at around 300C and
shows maximum intensity at 668C.
The amount of CO
2
is very small. Most
probably there are some impurities
of organic material, hydrocarbons or
carbonates. Even during storage in an
air atmosphere some carbonates could
be formed due to the small grain size of
the material.
the glass transition. The correlation
between the two data sets is excellent.
Waste Surrogates
Thermal Diffusivity and Specic Heat of a Waste Glass
Evolved Gas Measurement on Surrogate Waste Material
38
Thermophysical Properties of Some Important
Nuclear Materials at Room Temperature
The properties given in this table are
intended to be used as estimates
only. Some are quite accurate while
others are less certain. Of course it
is well known that small changes in
stoichiometry, porosity, microstructure,
etc. can have a profound effect on the
thermophysical properties. As a result,
NETZSCH does not guarantee the
accuracy of these values.
Pu 6.7 0.145 19.816
PuC 6.9 0.176 -
PuN 9.6 - 14.400
PuO
2
6.3 0.240 11.460 th.
Th 54.0 0.118 11.700
ThO
2
13.0 0.235 9.110 th.
U 27.6 0.116 19.070
U-14%Zr 18.5 - -
U-91%Zr 7.4 - -
(U
0.8
Pu
0.2
)O
2
8.9 @ th. 0.240 11.660 th.
UC 25.3 0.200 13.630 th.
UN 13.0 0.190 14.300 th.
UO
2
8.7 @ th. 0.235 10.960 th.
Fuels
Material
Property
(W/mK) C
p
(J/gK) (g/cm
3
)
InX-750 11.7 0.439 8.510
Low Cr Steel 42.3 0.442 7.858
Nichrome 12.0 0.420 8.400
SS-304 14.9 0.477 7.900
SS-316 13.4 0.468 8.238
Zirc2 17.0 0.290 6.550
Zirc4 14.1 0.293 6.580
Zr-2.5%Nb 19.0 0.315 6.570
Structural
Material
Property
(W/mK) C
p
(J/gK) (g/cm
3
)
Al
2
O
3
36.0 0.765 3.970
MgO 60.0 0.929 3.770
Si
3
N
4
16.0 0.691 2.700
SiC 120.0 0.675 3.160
ZrC 26.3 0.378 6.730
ZrN 10.5 (80-90%th.) 0.386 7.090
ZrO
2
(Y-stab.) 1.9 0.455 5.680
Miscellaneous
Material
Property
(W/mK) C
p
(J/gK) (g/cm
3
)
39
Ag 429.0 0.235 10.500
Al 237.0 0.903 2.702
Cd 96.6 0.231 8.650
Ce 11.3 0.192 6.770
Cr 93.7 0.449 7.160
Fe 80.2 0.447 7.870
In 81.8 0.267 7.310
Mg 156.0 1.024 1.740
Mo 138.0 0.251 10.240
Nb 53.7 0.265 8.570
Ni 90.7 0.444 8.900
V 30.7 0.489 6.100
W 174.0 0.132 19.300
Zr 22.7 0.278 6.570
Additional elements
Material
Property
(W/mK) C
p
(J/gK) (g/cm
3
)
AgInCd 60.0 0.230 10.170
B 27.0 1.107 2.500
B
4
C 92.0 0.960 2.520
BN 28.7 0.848 2.250
Hf 22.3 0.363 13.090
HfB
2
22.6 0.396 11.200
Ta 57.5 0.140 16.600
ZrB
2
23.0 0.230 6.090
Absorbers
Material
Property
(W/mK) C
p
(J/gK) (g/cm
3
)
Be 200.0 1.825 1.850
BeO 270.0 1.030 3.000
D
2
O 0.560 4.230 1.100
Graphite 100.0 0.710 1.700
H
2
O 0.561 4.217 1.000
ZrH
1.8
34.0 0.410 5.620
Moderators
Material
Property
(W/mK) C
p
(J/gK) (g/cm
3
)

s
o
u
r
c
e
s
:

d
i
v
e
r
s
e
40
Our Expertise
Service
All over the world, the name NETZSCH
stands for comprehensive support and
expert, reliable service, before and
after sale. Our qualied personnel from
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To maintain and protect your
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41
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Our philosophy is to continuously
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At NETZSCH, we convert the impossible
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42
Our Expertise

Applications Laboratories
The NETZSCH Thermal Analysis
Applications Laboratories are a
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43
Notes
N
G
B

C
h
a
r
a
c
t
e
r
i
z
a
t
i
o
n

o
f

N
u
c
l
e
a
r

M
a
t
e
r
i
a
l
s

E
N

7
0
0

0
2
1
4

L
H

T
e
c
h
n
i
c
a
l

s
p
e
c
i
f
i
c
a
t
i
o
n
s

a
r
e

s
u
b
j
e
c
t

t
o

c
h
a
n
g
e
.
NETZSCH-Gertebau GmbH
Wittelsbacherstrae 42
95100 Selb
Germany
Tel.: +49 9287 881-0
Fax: +49 9287 881 505
at@netzsch.com
When it comes to Thermal Analysis, Calorimetry (adiabatic & reaction) and the
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