B. Roduit (1), P. Guillaume (2), S. Wilker (3), P. Folly (4), A. Sarbach (4), B. Berger (4),

1
Estimation of Life Assessment of Energetic
Materials using Advanced Kinetic Elaboration of
HFC Signals
B. Roduit (1), P. Guillaume (2), S. Wilker (3),
P. Folly (4), A. Sarbach (4), B. Berger (4), J.
Mathieu (4), M. Ramin (5), B. Vogelsanger
(5) (1) AKTS AG, http//www.akts.com, TECHNOArk
3, 3960 Siders, Switzerland (2) PB Clermont s.a.,
http//www.pbclermont.be, Rue de Clermont 176,
4480 Engis, Belgium (3) Bundeswehr Institute for
Materials (WIWEB), Grosses Cent, 53913
Swisttal-Heimerzheim, Germany (4) armasuisse,
Science and Technology, http//www.armasuisse.ch,
3602 Thun, Switzerland (5) Nitrochemie Wimmis AG,
http//www.nitrochemie.com, 3752 Wimmis,
Switzerland
ESTAC - 10 22 - 27 August 2010 Rotterdam The
Netherlands
www.pbclermont.be
www.akts.com
www.armasuisse.ch
www.nitrochemie.com
www.bwb.org
2
DSC
TG

• The precise prediction of the degradation of
  materials

CL
HFC
HPLC
3
DSC
TG

• The precise prediction of the degradation of
  materials

CL
HFC
HPLC
4

• More precise measurement
• of the
• thermal aging
• of
• energetic materials
• Applications of
• isothermal microcalorimetry
• (HFC)

5
DSC
TG

• The precise prediction of the degradation of
  materials

CL
HFC
HPLC
6
DSC
TG

• The precise prediction of the degradation of
  materials

CL
HPLC
7

• Experimentally
• Just few temperatures

8
APPLICATION OF HFC
The use of HFC enables to gain advanced knowledge
on the reaction rate at the early stage of the
decomposition
experiments
T3
T2
T1
9
Well defined
50C
Because baseline is well defined
Well defined
7 years !
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Isoconversional methods

• Uncertainity of thermokinetic analysis the
  stages and
• physico-chemical reaction pathways are generally
  unknown

• What do you see below? Young women? Old
  man?
• Or both?

?
Observed thermal event can be the sum of thermal
events created during certain stages of the
reaction which are not always known
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Isoconversional method

• Isoconversional methods (model free)
• Three main modifications of isoconversional
  method are applied in the literature
• - Differential (Friedman)
• - Integral (Flynn-Ozawa-Wall)
• - Advanced integral based on non-linear procedure
  (Vyazovkin)

Differential isoconversional method
Reaction rate expressed by the Arrhenius equation

Reaction rate at a given reaction progress a
is only a function of the temperature A(a)
and E(a) are the pre-exponential factor and
apparent activation energy
12
Activation energy E as a function of the heat
release
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THERMAL AGING
14
THERMAL AGING
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The assumption that the reaction rate da/dt at
a given reaction progress a is only a function
of the temperature (differential isoconversional
analysis) is acceptable.

It can be applied for a precise life assessment
of energetic materials
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Conclusion
?
HFC
DSC
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Conclusion
If you want to perform fast experiments (DSC) and
get long term predictions using thermokinetics do
not expect very precise predictions. If you want
to perform fast experiments (DSC) and get very
precise predictions using thermokinetics do not
expect long term predictions. If you want to
achieve long term predictions and expect very
precise predictions using thermokinetics do not
perform fast experiments (DSC). Do long term
isothermal microcalorimetric measurements (HFC)
and perform thermokinetics.
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Conclusion
?
HFC
DSC
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Acknowledgements Our partners and friends

Thank you for your attention
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