Journal of Nuclear Materials 396 (2010) 294–302

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Journal of Nuclear Materials

journal homepage: www.elsevier.com/locate/jnucmat

Review

Pyrophoric behaviour of uranium hydride and uranium powders

F. Le Guyadec a,*, X. Génin a, J.P. Bayle a, O. Dugne b, A. Duhart-Barone c, C. Ablitzer c
a
CEA Marcoule DEN/DTEC/SDTC, 30207 Bagnols sur Cèze, BP 17171, France
b
DEN/DTEC/SGCS, 30207 Bagnols sur Cèze, BP 17171, France
c
CEA Cadarache DEN/DEC/SPUA, 13108 St. Paul lez Durance, France

a r t i c l e i n f o a b s t r a c t

Article history: Thermal stability and spontaneous ignition conditions of uranium hydride and uranium metal fine pow-
Received 1 September 2009 ders have been studied and observed in an original and dedicated experimental device placed inside a
Accepted 10 November 2009 glove box under flowing pure argon. Pure uranium hydride powder with low amount of oxide
(<0.5 wt.%) was obtained by heat treatment at low temperature in flowing Ar/5%H2. Pure uranium pow-
der was obtained by dehydration in flowing pure argon. Those fine powders showed spontaneous ignition
Keywords: at room temperature in air. An in situ CCD-camera displayed ignition associated with powder tempera-
Uranium
ture measurement. Characterization of powders before and after ignition was performed by XRD mea-
Hydride
UH3
surements and SEM observations. Oxidation mechanisms are proposed.
Ignition Ó 2009 Elsevier B.V. All rights reserved.
Oxidation
Synthesis
Characterization

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
2. Materials and experimental device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
3. Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
3.1. Synthesis of pure uranium hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
3.2. Synthesis of pure uranium powder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
3.3. Ignition of uranium hydride in air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
3.4. Ignition of uranium powder in air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
3.5. Characterization of final products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
4. Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302

1. Introduction Further studies are now going on concerning other uranium-

base powders especially uranium hydride and fine uranium pow-
In order to investigate uranium (metal) and uranium com- ders obtained from UH3 thermal dissociation. Synthesis conditions
pounds behaviour under oxidizing atmosphere, CEA research has in the range of several grams and powder characterization are first
already concerned uranium mononitride and uranium monocar- described. Handling uranium hydride imposed working in an inert
bide powders reaction in flowing air and argon or nitrogen with atmosphere, with very low amounts of oxygen and moisture, be-
different amounts of oxygen [1,2]. Parameters as grain size, heating cause of its extremely high thermal instability and its ignition un-
rate, temperature and elaboration conditions have been studied. der oxidizing atmospheres. Experimental device was specifically
Such powders often show pyrophoric behaviour, sometimes at set up in order to maintain amounts of UH3 or U powders under
low temperatures [3,4]. pure inert gas and to carry out ignition tests on several grams un-
der controlled atmosphere, without pre-oxidation.
* Corresponding author. Tel.: +33 04 66 33 93 12; fax: +33 04 66 79 66 25. The originality of the present study consists in the thermal
E-mail address: fabienne.leguyadec@cea.fr (F. Le Guyadec). instability of fine powders and their spontaneous ignition in air

0022-3115/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnucmat.2009.11.007
 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302 295

being observed with a CCD-camera placed above the crucible out- 2. Materials and experimental device
side the furnace. Sample temperature was measured with thermo-
couples directly placed inside the powder layer. Uranium base-material was used in the form of small thin mil-
The synthesis conditions of UH3 powders such as temperature, limetric plates about 20 mg each. After treatment in nitric acid
gas composition, flow rate, processing time, are not well based. 3.5 N solution during 12 min to avoid oxide-scale on uranium sur-
Hausner and Zambrow [5] indicates 175–225 °C temperature range face, the plates were exposed to flowing 0.5 L min1 argon contain-
as an optimal level for obtaining pure uranium hydride in flowing ing 5% hydrogen, during 10 h at 192 °C. Temperature was reached
pure hydrogen. Small amount of oxygen in hydrogen process gas is with a rate of 10 °C min1. Platelets were hydrated in a stainless
known to delay the start of the reaction. Maximum reaction rate steel 30 mm diameter crucible which was heat-treated in argon
lays around 225 °C. Higher reaction rates can be obtained with during 4 h at 300 °C before hydration to avoid oxygen pollution.
higher hydrogen pressures. Above 225 °C, hydration kinetics be- In those conditions quantitative hydration of uranium metal could
come progressively lower and uranium grains obtained by decom- be obtained for sample mass around 5 g.
position of hydride may appear under vacuum. At higher Fine uranium powder could be obtained by heat treatment of
temperature, uranium particles formed during decomposition of previous UH3 powder in the same flowing conditions but in
hydride may sinter in vacuum. pure argon, during 10 h at higher temperature 250 °C, allowing
The reverse reaction between uranium and hydrogen becomes dehydration. A 30 mm diameter crucible was used as for UH3
significant above 225 °C for Stakebake [6]. Albrecht and Mallett synthesis.
[7] shows maximum reaction velocity at about 280 °C and Hashino Both experiments were performed inside a kanthal-resistor fur-
and Okajima [8] indicates 268 °C as a limit temperature. Rate de- nace allowing maximal temperature of 500 °C. The furnace was
crease at higher temperatures is due to decomposition reaction placed inside a glove-box with very low leak rate <5.104 h1.
hindering the hydration reaction process. Alire studies [9] show Glove-box was maintained in flowing pure argon recycled with
that induction times could be eliminated by using high purity an inerting unit after removal of oxygen and water vapor. Two
gases. Induction effects caused by surface oxide films may be elim- purification reactors (purification reactor consisting in a molecular
inated in high vacuum [10]. Furthermore, Condon [10] indicates sieve for water vapor and in copper for oxygen impurity) allowed
dehydration kinetics in the range 200–300 °C. Many studies have very small concentrations ranging between 2 and 8 ppm. This
been done with uranium bulk material. Hashino [8] and Condon experimental specificity was necessary for handling fine reactive
[10] studied uranium coupons. powders as uranium hydride to prevent them from oxygen before
Uranium hydride occurs from following reaction: controlled heat-treatment in the furnace. It allowed obtaining very
1
small amounts of oxide in UH3 and U powders.
U þ 3=2H2 ! UH3 ; with DHr ¼ 127 kJ mol Ignition tests were performed in the same furnace under differ-
ent oxidizing atmospheres and especially in air. Samples were ex-
This reaction is reversible and decomposition of UH3 can occur
posed to flowing gas rates until 10 L min1. Round 2 g of uranium
under specific conditions.

UH3

4000

UH3
3000
Lin (Counts)

UH3
2000 UH3

Ta
UH3
1000 UH3 UH3 UH3

0
20 30 40 50 60 70
2-Theta - Scale
CONDA Essai n°19 - File: X6790.raw - Type: 2Th/Th locked - Start: 20.000 ° - End: 80.000 ° - Step: 0.015 ° - Step time: 19.9 s - Temp.: 25 °C (Room) - Time Started: 7 s - 2-Theta: 20.000 ° - Theta: 10.000 ° - Chi: 0.00 ° - Phi: 0.00
Operations: X Offset -0.075 | X Offset -0.063 | Background 1.000,1.000 | Import
00-004-0788 (*) - Tantalum - Ta - Y: 19.11 % - d x by: 1. - WL: 1.5406 - Cubic - a 3.30580 - b 3.30580 - c 3.30580 - alpha 90.0 00 - beta 90.000 - gamma 90.000 - Body-centered - Im-3m (229) - 2 - 36.1268 - I/Ic PDF 4.4 - F8=110(0
00-040-1313 (I) - Uranium Hydride - UH3 - Y: 78.03 % - d x by: 1. - WL: 1.5406 - Cubic - a 6.63890 - b 6.63890 - c 6.63890 - al pha 90.000 - beta 90.000 - gamma 90.000 - Primitive - Pm-3n (223) - 8 - 292.609 - F24= 9(0.0601,43)
00-041-1422 (*) - Uraninite-C - UO2 - Y: 1.12 % - d x by: 1. - WL: 1.5406 - Cubic - a 5.46700 - b 5.46700 - c 5.46700 - alpha 9 0.000 - beta 90.000 - gamma 90.000 - Face-cente red - Fm-3m (225) - 4 - 163.398 - F9= 77(0.0130,9)

Fig. 1. Uranium hydride powder obtained after heat-treatment of uranium plates in Ar–5%H2 and XRD analysis.
296 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302

hydride or uranium powder was placed inside a stainless steel 3. Results

15 mm diameter and 0.2 mm thick crucible. The experimental de-
vice allowed viewing material behaviour during heating and igni- 3.1. Synthesis of pure uranium hydride
tion through viewports and registering with a CCD camera.
Continuous temperature measurements at various points of the After heat treatment under flowing Ar/5%H2, uranium plates
powder were registered with K-thermocouples placed inside the were transformed into a fine black uranium hydride powder.
sample. A two-color optical pyrometer was used to measure sam- Quantitative hydration of uranium metal could be obtained for
ple surface temperature in the range from 1000 to 3000 °C. Pres- sample mass around 5 g. Fig. 1 shows uranium hydride powder
sure measurement inside the furnace was also registered. The after synthesis in the furnace. Small amount of this powder (nearly
sample was heated at 5 °C min1 up to 500 °C, after which the tem- 30 mg) was then prepared in pure argon inside the glove-box for
perature was maintained constant at 500 °C during 30 min before XRD analysis. Powder was placed inside a specific and tight sample
cooling at 10 °C min1 down to ambient temperature. holder from Brucker under argon. So, the obtained powder could be

Fig. 2. Uranium hydride grains observed by scanning electron microscopy (X250 left and X16000 right).

1300

1200
Ta
1100

1000 U
900

800
U Ta
Lin (Counts)

700 U
600

500 U U
400
Ta
300 U
200 U
100

0
21 30 40 50 60 70
2-Theta - Scale
CONDA essai 30 - File: X6820.raw - Type: 2Th/Th locked - Start: 20.000 ° - End: 80.000 ° - Step: 0.015 ° - Step time: 19.9 s - Temp.: 25 °C (Room) - Time Started: 15 s - 2-Theta: 20.000 ° - Theta: 10.00
Operations: X Offset 0.037 | Background 0.098,1.000 | Import
00-004-0788 (*) - Tantalum - Ta - Y: 75.60 % - d x by: 1. - WL: 1.5406 - Cubic - a 3.30580 - b 3.30580 - c 3.30580 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - Im-3m (229) - 2 - 36.12
03-065-2477 (I) - Uranium - U - Y: 67.16 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 2.85800 - b 5.87600 - c 4.95500 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered - Cmcm (63) - 4 - 8

Fig. 3. Uranium fine powder after heat treatment in argon at 250 °C and XRD analysis.
 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302 297

analyzed in non-oxidizing atmosphere on a Brucker D8 XRD device

allowing observation of the real formed phases. The resulting XRD
pattern (Fig. 1) showed only uranium hydride peaks. Only very few
uranium oxide UO2, lower than 1 wt.%, was detected by Rietveld
pattern fitting. Tantalum peaks appeared because small amount
was added to the hydride powder to calibrate the pattern.
Furthermore, grain size measurements by scanning electron
microscopy showed two grain sizes inside the UH3 powder. Small
randomly shaped grains (a few lm) could be observed (Fig. 2) as
well as large tabular grains (10–50 lm). This last population of
grains appears with elongated angular platelets, all oriented in
the same direction and sharp ridges (Fig. 2).

3.2. Synthesis of pure uranium powder

Uranium hydride was transformed into fine grained pure ura-

nium powder after dehydration by heat treatment in pure argon
at 250 °C in the furnace. Sample mass was around 3 g. Powder
was dark black and sometimes agglomerated into small amounts. Fig. 5. First step of ignition: flash of lightning above the sample surface.
Fig. 3 shows uranium powder inside the glove-box. Small amount
of this powder was analyzed by XRD with the same tight sample
holder as the uranium hydride before and with the same experi-
mental protocol. Fig. 3 shows the XRD pattern with uranium peaks,
no more hydride peaks and with very few UO2 (lower than 1 wt.%).
Grain size was observed by SEM and showed aspects close to
those of the uranium hydride. The U fine powder was constituted
with small grains (a few lm) and large tabular ones (10–50 lm)
as seen in Fig. 4. It shows oriented structure with a morphology
of fine agglomerated platelets as already observed for the uranium
hydride grains before decomposition.

3.3. Ignition of uranium hydride in air

The powder sample about 2.3 g was placed inside a cylindrical

stainless steel 15 mm diameter crucible. The sample was a 5 mm
thick powder bed containing two K-type thermocouples for contin-
uous monitoring of sample temperature during heat-treatment
and ignition. The ignition test was performed in flowing air at a
rate of 10 L min1. Before air was introduced in the furnace cham-
ber, the sample was exposed to flowing pure argon during 10 min
at room temperature. After switching to air atmosphere, the pow- Fig. 6. Second step of ignition combustion in the solid phase.
der sample was maintained at room temperature during five more
minutes. Afterwards, the sample was subjected to heating at
5 °C min1 up to 500 °C in air, temperature was maintained con- the sample bed for about 10 s immediately followed by the appa-
stant at 500 °C during 30 min and finally sample was cooled at rition of an orange flame at the sample surface. In the same mo-
10 °C min1 until room temperature. Final atmosphere was again ment, a pressure variation round 15 mb was registered inside the
pure argon. furnace chamber. After this first step of gaseous combustion, a sec-
For 2.3 g of pure, dry and fresh uranium hydride, ignition was ond step followed recognized by a solid combustion at the surface
observed shortly after air was introduced while sample was still of the powder bed, running from the center of the free sample
at room temperature. It occurred with a flash of lightning above interface to the outer boarder of the crucible, and furthermore to

Fig. 4. Uranium grains observed by scanning electron microscopy (X250 left and X16000 right).
298 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302

the bulk of the material. It must be noted that the volume of the combustion, to reach finally two or three times the initial thickness
powder bed significantly increased during ignition and during solid after heating until 500 °C.

1000

900 sample temperature

regulation temperature

800

700

600
Final product
temperature (°C)

500

400

300

200

100

0
-500 0 500 1000 1500 2000 2500 3000 3500 4000 4500 50

time (s)

Fig. 7. Sample temperature measurement: temperature rise at ignition and during heating, volume increase after test in air.

1000 1030
air introduction

900 sample temperature

regulation temperature
1025
furnace pressure
800

1020
700
sample
600
temperature (°C)

pressure (mb)

1015

500

1010
400

300
1005
pressure

200

1000
100

0 995
-200 -100 0 100 200 300 400
time (s)

Fig. 8. Temperature peak at ignition and pressure variation inside the furnace.
 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302 299

Ignition corresponded to a brief temperature rise (the thermo-

couple placed inside the sample reached 863 °C) and temperature
was still high (above 300 °C) during the solid combustion step dur-
ing nearly 15 min. The first temperature peak occurred while sam-
ple was still at room temperature. After the solid combustion,
uranium hydride is still present in the powder sample and uranium
oxides UO2 and U3O8 were formed, analyzed by XRD. The presence
of U3O8 even at a low temperature of furnace regulation can be ex-
plained by the high temperature shortly reached during ignition
(nearly 1000 °C). A second exothermic phenomenon, with lower
intensity, occurred during heating, when the sample reached
nearly 300 °C and can be attributed to final transformation into
U3O8 oxide. The sample combustion is shown in Figs. 5 and 6. Tem-
perature and pressure monitoring are presented in Fig. 7 (all the
test) and Fig. 8 (focused on the first ignition step). XRD pattern
of the reaction product just after ignition is shown in Fig. 9, volume
increase and final product after heating until 500 °C in Fig. 7.

Fig. 10. Uranium powder ignition: combustion in the solid phase.

3.4. Ignition of uranium powder in air

In the same experimental conditions pure fresh and dry ura- 3.5. Characterization of final products
nium powder was tested. A 5 mm thick powder bed with 2.8 g of
uranium was exposed to air in the furnace, after 10 min under After ignition test and cooling to room temperature, XRD pat-
flowing pure argon. As well as in the case of uranium hydride, igni- tern showed only uranium oxide U3O8 (Fig. 12) both from UH3
tion occurred shortly after air introduction into the furnace, at and U powder oxidized in air at 500 °C. The second temperature
room temperature. No flash of lightening was observed, only solid peak observed nearly 300 °C corresponded to complete transfor-
combustion occurred with uranium powder (Fig. 10). Sample tem- mation of the residual hydride or uranium and UO2 into U3O8
perature was still near 200 °C during several minutes. No significa- oxide. U3O8 grains were observed by scanning electron micros-
tive pressure variation was noticed in the furnace during the copy. Grains obtained from UH3 ignition are keeping the form of
ignition. Temperature and pressure monitoring are presented in platelets with memory of the initial grain structure of the uranium
Fig. 11. Final product was again U3O8. hydride. Some smoothening appears at the surface of the elongated

UO2
U3O8 U3O8
U3O8
600

Ta

UH3
500

U3O8

400
Lin (Counts)

UO2
300
UO2
Ta

U3O8
200
U3O8
U3O8 U3O8

100 UH3

0
20 30 40 50 60 70
2-Theta - Scale
CONDA essai n°20 - File: X6898.raw - Type: 2Th/Th locked - Start: 20.000 ° - End: 79.820 ° - Step: 0.015 ° - Step time: 19.9 s - Temp.: 25 °C (Room) - Time Started: 13 s - 2-Theta: 20.000 ° - Theta: 10.000 ° - Chi: 0.0
Operations: X Offset -0.212 | X Offset -0.228 | Smooth 0.106 | Background 1.000,1.000 | Import
00-004-0788 (*) - Tantalum - Ta - Y: 76.20 % - d x by: 1. - WL: 1.5406 - Cubic - a 3.30580 - b 3.30580 - c 3.30580 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - Im-3m (229) - 2 - 36.1268 - I/Ic PDF 4
04-007-2522 (N) - Uranium Oxide - UO2.12 - Y: 100.47 % - d x by: 1. - WL: 1.5406 - Cubic - a 5.44100 - b 5.44100 - c 5.44100 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fm-3m (225) - 4 - 161.07
00-031-1425 (C) - Uranium Oxide - U3O8 - Y: 135.16 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 6.81200 - b 6.81200 - c 4.14200 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P-62m (189) - 1 - 166.452
00-040-1313 (I) - Uranium Hydride - UH3 - Y: 52.66 % - d x by: 1. - WL: 1.5406 - Cubic - a 6.63890 - b 6.63890 - c 6.63890 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - Pm-3n (223) - 8 - 292.609 - F24=

Fig. 9. XRD pattern just after ignition of UH3 in air.

300 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302

1000 1035
air introduction
sample temperature
900 regulation temperature
furnace pressure 1030

800
sample
1025
700

600
température (°C)

1020
pressure

pressure (mb)
500

1015
400

300
1010

200

1005
100

0 1000
-200 0 200 400 600 800 1000
time (s)

Fig. 11. Sample temperature measurement: temperature rise at ignition and during solid combustion.

2800
U3O8 U3O8
2700
2600
2500
2400
2300
2200 U3O8
2100 Ta
2000
1900
1800
1700
Lin (Counts)

1600
1500
1400
1300
1200
1100
1000 U3O8
900
800
700
600 U3O8 U3O8 U3O8
500
400
300
200
100
0
20 30 40 50 60 70
2-Theta - Scale
CONDA Essai n°23 - File: X6799.raw - Type: 2Th/Th locked - Start: 20.000 ° - End: 80.000 ° - Step: 0.015 ° - Step time: 19.9 s - Temp.: 25 °C (Room) - Time Started: 14 s - 2-Theta: 20.000 ° - Theta: 10.000 ° - Chi: 0.00 ° - Phi: 0.00
Operations: X Offset -0.131 | X Offset -0.131 | Background 1.000,1.000 | Import
00-004-0788 (*) - Tantalum - Ta - Y: 28.66 % - d x by: 1. - WL: 1.5406 - Cubic - a 3.30580 - b 3.30580 - c 3.30580 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - Im-3m (229) - 2 - 36.1268 - I/Ic PDF 4.4 - F8=110(0.
00-040-1313 (I) - Uranium Hydride - UH3 - Y: 8.93 % - d x by: 1. - WL: 1.5406 - Cubic - a 6.63890 - b 6.63890 - c 6.63890 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - Pm-3n (223) - 8 - 292.609 - F24= 9(0.0601,43)
00-031-1424 (C) - Uranium Oxide - U3O8 - Y: 157.57 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 6.71600 - b 11.96000 - c 4.14700 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered - C2mm (38) - 2 - 333.101 - I/Ic P

Fig. 12. XRD pattern after ignition of uranium in air: U3O8 oxide.
 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302
Fig. 13. Grains observed by scanning electron microscopy (X16000) after UH3
ignition in air.
Fig. 14. Grains observed by scanning electron microscopy (X16000) after U ignition
in air.
platelets and compared to the initial grains, ridges are less angular,
grains are rounded up (Fig. 13). Grains obtained from U powder
ignition are most of the time round grains with less memory of
the initial platelets structure than in the case of UH3 ignition
(Fig. 14).
4. Interpretation
Experimental results about ignition in air of uranium hydride
and uranium fine powders could be observed, monitored with a
CCD camera and sample temperature could be registered continu-
ously during ignition and heating. Ignition steps could clearly be
identified.
Uranium hydride ignited through a two-step process including
gaseous combustion with a brief flash of lightning and a flame at
the sample surface in the beginning of the ignition, followed by a
solid phase combustion step first at the surface and then inside
the bulk of the powder bed during several minutes. Sample tem-
perature rise until 860 °C and above was registered and during
the solid combustion phase sample temperature was still main-
tained above 300 °C for several minutes. Ignition occurred at ambi-
ent temperature as soon as air was introduced inside the furnace.
301
For uranium powder bed in the same experimental oxidizing
conditions, only the second step occurred: a solid phase combus-
tion at the surface and inside the powder bed was observed. Again
brief temperature rise was registered followed by several minutes
near 200 °C and above, before sample temperature came back to
furnace regulation temperature.
Oxidation of uranium hydride is strongly exothermic, with high
reaction heat release:
1
UH3 þ 7=4O2 ! UO2 þ 3=2H2 O; with DHr ¼ 1386 kJ mol
Uranium powder reaction in air is also highly exothermic:
1
U þ O2 ! UO2 ; with DHr ¼ 1129 kJ mol
These reactions occur faster with small grain size. The high val-
ues of reaction heat explain the observed ignition phenomenon.
Based on these experimental results, following oxidation mech-
anism can be proposed:
– reaction with air of the small amount of uranium in equilibrium
with uranium hydride present at the sample surface at the
beginning of the test (partial oxidation),
U þ O2 ! UO2
– heat produced by this exothermic oxidation reaction induces
dehydration of uranium hydride which can occur quantitatively
in the powder sample,
UH3 ! U þ 3=2H2 ;
– hydrogen formation explains the combustion in the gaseous
phase that was observed in the case of UH3 in air, with a flame
in presence of hydrogen and oxygen,
– oxidation in air of the uranium formed after decomposition of
hydride (quantitative oxidation),
U þ O2 ! UO2 ;
– and finally, complete transformation follows: UO2 þ 1=3O2 !
1=3U3 O8 .
5. Conclusions
The UH3 powder that was obtained in this study by heat treat-
ment at low temperature in flowing Ar/5%H2 was very pure hy-
dride as proved by XRD and Rietveld analysis. UH3 grains were
not surrounded with any small oxide layer which could protect
the hydride, avoid further oxidation and prevent from ignition at
low temperatures in air. This point can specially explain the igni-
tion we observed at room temperature. Mass of the sample (a
few grams) and the configuration of a powder bed well exposed
to the flowing air can also explain this point. Oxygen could easily
reach the powder.
Uranium fine and pure powders could be obtained by low tem-
perature heat treatment in pure argon and short operating times.
The PYRO test setup, with its low O2 and H2O amounts continu-
ously controlled and maintained inside the glove-box, allows many
applications concerning very reactive materials which must be
protected from air. CEA continues to conduct active research on
the pyrophoric behaviour of U-base materials, including materials
for future nuclear cycle.
Spontaneous ignition was achieved at room temperature when
uranium hydride or metallic uranium fine powders are freshly syn-
thesized and kept away from oxygen and moisture.
302 F. Le Guyadec et al. / Journal of Nuclear Materials 396 (2010) 294–302

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