Journal of Nuclear and Radiochemical Sciences, Vol. 6, No. 3, pp. 211-214, 2005

Tc Carbide and New Orthorhombic Tc Metal Phase
K. E. German,*, a V. F. Peretrukhin,a K. N. Gedgovd,a M. S. Grigoriev,a A. V. Tarasov,aYu. V. Plekhanov,a A. G. Maslennikov,a G. S. Bulatov,a V. P. Tarasov,a and M. LecomtebabA.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky pr. 31, 119991 Moscow, Russia
DEN/DRCP/SCPS CEA-Marcoule, BP 17171, 30207 Bagnols sur Ceze Cedex France

Received: July 31, 2005; In Final Form: September 30, 2005
Tc metal and metal-like carbide phases are revisited with special attention given to Tc-rich phases in the view ofprospective nuclear fuel utilization and alternative transmutation targets fabrication. A new Tc-metal phase has
been found and new softer conditions for the Tc carbide formation were observed. The unit cell parameters of anew orthorhombic Tc metal were a = 2.805(4), b = 4.958(8), c = 4.474(5)Å (V/z = 15.55 Å3) for Tc-C with 1.38
wt.% C and a = 2.815(4), b = 4.963(8), c = 4.482(5) Å (V/z = 15.65 A3) for Tc-C with 1.96 wt.% C.

1. Introduction
Tc metal-like carbide phases and mixed Tc-Ac-C and (Tc/
Mo)-Ac-C carbide have got new sound in the view of prospective nuclear fuel utilization. The published data on the preparation and properties of technetium carbide are not enoughsufficient for the prediction of technetium behavior in the uranium carbide nuclear fuel during and after the irradiation in
nuclear reactors as well as for the consideration of the alternative to pure metal targets for technetium transmutation.1−5 Werevisited these studies with special attention given to Tc-richphase diagram triangle. Here we report on the new Tc-metal
phase found and new softer conditions of Tc carbide formation.
2. Experimental
The initial metal technetium was prepared by reduction ofsynthetic (CH3) 4NTcO4 in Ar-6% H2 gas in a gas-flow tubular
furnace at 500 ˚C followed with annealing just only at 800 ˚C
to avoid microparticle adhesion. As the metal samples were Xray amorphous, the ESCA spectra were applied to support theformation of Tc-metal phase (Figure 1) with reference to.8
The resulting Tc metal was finely grinded and the fine fraction from 20 to 50 micrometer in diameter was sieved for theexperiment.
The samples of 500 mg of Tc metal were vigorously
grounded together with the desired quantity of ultra-pure carbon and pressed at p = 1 ton/cm 2 giving the resulting 5 mmthick pellets that were annealed in high temperature vacuum
furnace at the temperatures 800 ˚C, 1000 ˚C and 1200 ˚C. The
annealing temperature was achieved in 1.5 hours. Annealing
time was two hours (in some cases also 8 hours) for each chosen temperature. After annealing accomplishing the samples
were cooled to room temperature in vacuum during 6–8 hours.
X-ray powder diffraction patterns were recorded directly fromthe pellet surfaces both before and after polishing.

Figure 1. ESCA spectrum of the Tc met prepared by reduction of(CH3) 4NTcO4 in Ar-6% H2 gas.

TABLE 1: Experimental Set for Tc -C Pellet Preparation
Sample
No

Tc,
mg

C,
mg

Tc,
wt.%

C,
wt.%

3
2
4
5
1

500
500
500
500
500

7
10
16
21
60

98.6
98.0
96.8
95.9
89.2

1.4
2.0
3.2
4.1
10.8

99

3. Results and Discussion
The pellets with variable Tc : C atomic ratio (see Table 1) wereprepared. The experiments were carried out aiming to study theinteraction of Tc metal with graphite at different Tc/C atomic
ratios as a function of annealing temperature.
*Corresponding author. E-mail: guerman@ipc.rssi.ru. FAX:
+7-495-335-1778.

Tc NMR (Bruker MSL-300, magnetic field 7.04 T, SF =67.55 MHz) and ESCA (HP 5950A) spectroscopy were used forthe analyses of Tc speciation. 13C NMR (also at Bruker MSL300) was used for the speciation of carbon (see Figure 2) inside
the pellets. Microhardness measurements have been carried out
with a diamond head test instrumentation and an optical microscope. The obtained results led to the conclusion on the formation of the biphasic composition that includes the technetium
carbide TcxC where (x > 1, in most cases 2 < x < 6) and the excesscarbon starting from 17 at.%.

© 2005 The Japan Society of Nuclear and Radiochemical Sciences
Published on Web 12/28/2005

212 J. Nucl. Radiochem. Sci., Vol. 6, No. 3, 2005

I, %German100

Grey bars : ref. hcp Tc metal
Curves: exp. spectra

75

B

50
25
0

30

40

50

60

70

80

90

100

I, %

75

A

50
25
0

30

40

50

60

70

80

90

2Theta, deg

Figure 3. X-ray Diffraction spectra of pellets Tc-C annealed for 8hours at 800 ˚C: A – 1.38 wt.% C; B – 1.96 wt.% C.
Figure 2. 13C-NMR spectrum of the non-destructed pellet (sample 1,
Tc : C = 1:1) of technetium carbide with graphite.

In the range of low carbon concentrations (Tc-C mixtures of
1–2 wt.% C, 10 to 15 at.% C) at 800 ˚C the formation of newly
found intermediate orthorhombic Tc metal was proved by X-ray
powder diffraction analyses (see Figure 3). The unit cell parameters were a = 2.805(4), b = 4.958(8), c = 4.474(5) Å (V/z =15.55 Å 3 ) for Tc-C with 1.38 wt.% C and a = 2.815(4), b =4.963(8), c = 4.482(5) Å (V/z = 15.65 Å3) for Tc-C with 1.96
wt.% C. The parameters of Tc could be explained by orthorhombic distortion of the well known hcp Tc metal structure a1 = a,b = a2 3 , c = c as shown at Figure 4.
The formation of similar phases most probably has takenplace under conditions used in references,2, 4 but the distortionof the lattice parameters determined in these references for the
Tc-rich phases were very much different one from another andin fact erroneous, although the parameters reported in the samereferences for the cubic technetium carbide and for Tc-U-C
carbide phases were correct (see also the discussion in).9This research shows that technetium carbide is being formed
somewhat easier if compared to previously known data,2, 4 indicating that its formation in the spent uranium carbide nuclear
fuel is quite possible.

Figure 4. Transformation of the initial hcp Tc metal cell to the new
orthorhombic cell : a1=a, b= a2 3 , c = c.

The fcc Tc carbide phase is defective in carbon. Some estimates of the boundary frames of Tc carbide composition wereobtained indicating the upper limiting ratio of about Tc : C = (5± 0.5) : 1 although the exact composition of Tc carbide could befurther précised.
The X ray diffraction study proved the formation of cubic
phase with a = 3.98 Å (Fm3m) in the interval of Tc : C ratiosfrom 1 : 1 to 5 : 1. The cubic Tc carbide phase was observed
already at T = 800 ˚C indicating that the conditions for its preparation could be much softer compared to that reported in.2, 4Micro-hardness of Tc carbide depends on the C content andthe temperature of preparation, and it is by the factor of 2–2.5

TABLE 2: Micro-hardness Measurements and X-ray Diffraction Tests for the Second Experimental Set for Tc -C Pellet
Preparation (Tc mass was 500 mg in each pellet)
Results of physical tests (X-ray powder diffraction, cell determination,
microhardness measurements) made after annealing at
800 ˚C
1000 ˚C
1200 ˚C

Samp.
No

C,
mg

C, wt.%

3

7

1.4

Tcmet, ortho, ↑V,
H = 278 kg/mm2

Tcmet, hexag., ↑V,
H = 255 kg/mm2

Tcmet, hexag., ↑V,
H = 476 kg/mm2

2

10

2.0

Tcmet, ortho, ↑V,
H = 304 kg/mm2

Tcmet, hexag., ↑V,
H = 284 kg/mm2

Tcmet, hexag., ↑V,
H = 529 kg/mm2

4

16

3.2

Tcmet, orto, ↑V,
H = 324 kg/mm2

Tcmet, hexag., ↑V,
H = 281 kg/mm2

Tcmet, hexag., ↑V,
H = 304 kg/mm2

5

21

4.1

TcxC +C, ~V,
Zone 1 : H = 327 kg/mm2
Zone 2 : H = 227 kg/mm2

TcxC +C, ~V,
Zone 1 : H = 304 kg/mm2
Zone 2 : H = 227 kg/mm2

TcxC +C, ~V,
Zone 1 : H = 461 kg/mm2
Zone 2 : H = 228 kg/mm2

1

60

10.8

TcxC +C, ~V,
Zone 1 : H = 320 kg/mm2
Zone 2 : H = 228 kg/mm2

TcxC +C, ~V,
Zone 1 : H = 320 kg/mm2
Zone 2 : H = 228 kg/mm2

TcxC +C, ~V,
Zone 1 : H = 470 kg/mm2
Zone 2 : H = 227 kg/mm2• V = Unit cell volume/Z; ↑V : specific unit cell volume per atom increases, ~V : specific unit cell volume is steady• H = microHardness.
• Tcmet : metal Tc is formed, ortho : orthorhombic Tc metal phase, hexag.: hcp Tc metal• TcxC + C : a mixture of Tc carbide and graphite is present

J. Nucl. Radiochem. Sci., Vol. 6, No. 3, 2005 213

Tc Carbide and New Orthorhombic Tc Metal Phase
X-ray diffraction spectrum of TcC

6000
5000

I

4000
3000
2000
1000
0

0

20

40

60

80

100

120

2ThetaFigure 5. Experimental X-ray diffraction pattern of Tc metal annealedwith 50 at.% C at 1150 ˚C for 8 hours (fcc TcC1-x produced + C x rest).
Figure 7. Typical model for fcc (a = 3.98 Å) virtual Tc metal 42atomic cluster filled with 7 carbon atoms.

liquidus of graphite in the Tc-C systems.
The Tc alloy with 17.5% (at.) C in the cast and annealed at
1400 ˚C according to4 and at 1150 ˚C according to6 conditions
had always a single-phase for structure of the metallic sub-lattice with the lattice periods close to 3.98(2) Å and V/z = 15.76
Å3 (Figure 6). This phase can be regarded as a virtual modification of cubic technetium metal stabilized with carbon or atechnetium carbide with the cubic lattice of the NaCl type (δphase) defective in carbon.
Figure 6. Tc metal/Tc carbide specific cell volume (V/z, per 1 Tcatom) as a function of C content.

higher compared to the micro-hardness of pure technetium metaland of newly found orthorhombic Tc metal phase (see Table 2).
Microanalyses of the polished section indicate the presenceof two phases: 1) the white phase presents a carbon-defective
technetium carbide TcxC where (x > 1, presumably (2 < x < 6)
while the black phase is non-reacted carbon. The X-ray pattern
supported the presence of these two phases (Figure 5).
The microhardness measurements at the white parts of thepellet the 17– 22% increase in comparison with hcp-technetium
metal foil, while the microhardness measurements at blacksites were characteristic of pure carbon.
Tc metal specific cell volume (per 1 Tc atom) increases by ~10% with the increase in C content from 1 to 20% and then presents a steady value (Figure 6). This is an important input data forthe design of the more stable phases for the further researches.
Analogous tests were carried out with Re metal. No changes
were observed in the structure of hexagonal Re-pattern, in
good agreement with7 and the higher melting temperature of
Re-metal (~3180.0 ˚C ~ 3453.15 ˚K) compared to Tc melting
temperature (2157 ˚C, modern values for the melting points areused, the corrected melting point for technetium becomes 2430
˚K. The peak of non-reacted graphite was also present in the
X-ray pattern of Re-C mixture.
The attempts were undertaken to characterize the samples oftechnetium carbide with 99Tc-NMR and 13C-NMR methods, thespectra were recorded at the non-destructed pellets. The 99Tc –NMR spectrum of the Tc : C = 1 : 1 sample was of medium quality and was roughly characterized with Knight shift of 1570 ppm(with reference to 0.1 M KTcO4 solution). This Knight shift isquite different from the one observed in pure Tc metal.10
The 13C-NMR spectrum of non-destructed pellet No 1 (withthe ratio Tc : C = 1 : 1) (see Figure 2) gave evidence for thepresence of intensive peak of non-reacted graphite at 114.16
ppm and a shoulder at 36.52 ppm that is attributed to the carbon present in the technetium carbide matrix.
Our findings are in good agreement with the predicted phase
Tc-C diagram in,1 that was based on the experimental resultsfrom 2−5 and taking into account the results of calculating the

4. Quantum Chemical Study
To analyze the stability of phases in Tc-C system the calculation was carried out by the non-empiric quantum chemistry
method XαDV using the program DVSCAT. Two cluster models with 18 and 42 metal atoms were studied (the latter presented at the Figure 7). The calculation results are given in the
Tables 3 and 4. The difference of y–y(0) = (IB (TcxC)–IB (Tcmetal)),
where I B –bounding index, was found to be the most sensitive
parameter for the description of the cluster stability. These calculations were supported with the graphical analyses at Figure
8, where zero line corresponds to pure metal cluster, positive∆IB values correspond to the increase in stability relative to Tc
metal, while the negative values – to the decrease in cluster stability. Although the experimental data were also approximatedwith a polynomial line (dotted), only qualitative sense wasattributed to that dotted line without any special consideration.
Both the calculations and the Figure 8 gave the evidence that:1) small amounts of carbon atoms addition (1–10 at.%) resultin the important increase of the cluster stability;2) the tendency of decrease in Tc carbide stability with anincrease of carbon content starts at least at 12% of C;3) the latter tendency is not monotonic but is characterized withsine-type dependency, the last stable maximum being close
to 17% C that corresponds to Tc 42 C 7 in the frame of ourmodel or to Tc6C in general infinite mode. The composite
with 26% C has much less probability and could doubtfully
be formed as also reported at.6
In conclusion these researches showed that technetium carbide is being formed much easier compared to previous data
most probably due to the formation of newly observed intermediate orthorhombic Tc metal phase. Its formation in the spentcarbide nuclear fuel became quite possible and would result in
important increase in specific cell volume and hence - in thespecific fuel volume.
5. Conclusions
1. A new Tc-metal phase has been found and new softer conditions for the Tc carbide formation were observed. The unit
cell parameters of a new orthorhombic Tc metal were a =214 J. Nucl. Radiochem. Sci., Vol. 6, No. 3, 2005

GermanTABLE 3: The Results of Quantum Chemistry Calculation by Method Xα DV Using the Program DVSCAT of the Cluster
Model with 42 Metal Tc Atoms in fcc Structure (binding order per atom, carbon to technetium ratio (C/Tc), number ofatoms in cluster (Nat), number of the bonds (Nbond ), number of the bonds per atom (Nbond per atom))
Model

Number of
C atoms

Bindingorder/atom

C/Tc

Nat

1/Nat

N bondN bond peratom

N bond of
TcTc type

N bondTcC/TcTc

Nelectrones

Tc42
Tc42C
Tc42CC
Tc42C_C
Tc42C3
Tc42[C3]
Tc42C4
Tc42C5
Tc42C6
Tc42C7
Tc42(C7)
Tc42C8
Tc42C9
Tc42C10
Tc42C11
Tc42(C11)
Tc42C12

0
1
2
2
3
3
4
5
6
7
7
8
9
10
11
11
12

1,13471,1402
1,1313
1,1323
1,14971,146
1,13491,1301
1,1254
1,1382
1,1327
1,119
1,1255
1,1294
1,1367
1,1355
1,109900,02380,0476
0,0476
0,0714
0,0714
0,09520,119
0,14290,1667
0,1667
0,19050,21430,2381
0,26190,26190,2857

42
43
44
44
45
45
46
47
48
49
49
50
51
52
53
53
54

0,02381
0,02326
0,02273
0,02273
0,022220,022220,02174
0,021280,02083
0,02040,02040,02
0,01961
0,01923
0,01887
0,01887
0,01852

144
150
156
156
162
162
168
174
180
186
179
190
192
201
201
196
207

3,43
3,49
3,55
3,55
3,60
3,60
3,65
3,70
3,75
3,80
3,65
3,80
3,76
3,87
3,79
3,70
3,83

144
144
144
144
144
144
144
144
144
144
137
142
138
141
135
130
135

0,00
0,04
0,08
0,08
0,13
0,13
0,17
0,21
0,25
0,29
0,31
0,34
0,39
0,43
0,49
0,51
0,53

1806
1812
1818
1818
1824
1824
1830
1836
1842
1848
1848
1854
1860
1866
1872
1872
1878

0,02

TABLE 4: The Results of Quantum Chemistry Calculation
by Method Xα DV Using the Program DVSCAT of the Cluster
Model with 42 Metal Tc Atoms in fcc Structure, N(C)/N(Tc):
The Ratio of Carbon Atoms Number to Tc Atoms Number,Mean Bond Strength in a Tc-C Cluster y(x) = I B (Tcx C),
y(0)–mean Bond Atrength in the Pure Tc Metal Cluster

I B(Tc xC) - I B(Tcmetal )

0,01

0,00

-0,01

-0,02

-0,03
0,00

0,05

0,10

0,15

0,20

0,25

0,30

0,35

CC, at. fraction
Figure 8. The ∆I = (IB(TcxC) - IB(Tc metal) increase in mean bond strength
relative to Tc metal, attributed to 1 cluster atom in Tc carbide withvariable C as a function of C content. IB(TcxC) – mean bond strengthin Tc carbide, IB(Tcmetal) – mean bond strength in Tc metal, CC- Carbon
concentration in the cluster in atomic fractions. Solid line: calculateddata, Dash and dot line: Tc metal level, dot line: the qualitative meantendency in the IB(TcxC) - IB(Tc metal) index value.
32.805(4), b = 4.958(8), c = 4.474(5)Å (V/z = 15.55 Å ) for
Tc-C with 1.38 wt.% C and a = 2.815(4), b = 4.963(8), c =4.482(5) Å (V/z = 15.65 A3) for Tc-C with 1.96 wt.% C.
2. Quantum chemistry consideration supported the high affinityof Tc to C at low C content and also several stability regionswith the last one situated at Tc/C ratio of approximately 6/1.
References(1) V. N. Eremenko, T. Ya. Velikanova, and A. A. Bondar, Soviet
Powder Metallurgy and Metal Ceramics 28, 868 (1989).
(2) W. Trzebiatowski and J. Z. Rudzinski, Z. Chem. 2, 158(1962).
(3) C.H. Rinehart and R. C. Behrens, J. Phys. Chem. 83, 2052
(1979).
(4) H. R. Heines, P. C. Mardok, and P. E. Potter, Plutonium 1975
and other Actinides, Proc.: 5th Int. Conf. (Baden Baden,1975). Amsterdam, pp. 233-244, (1976).
(5) A. L. Giorgi and E. G. Szlarz, J. Less-Common Metals 11,455 (1966).
(6) V. F. Peretrukhin, K. E. German, and M. Lecomte et. al.

Numberof carbon
atoms
Tc42
0
Tc42C
1
Tc42CC2
Tc42C_C
2
Tc42C3
3
Tc42[C3]
3
Tc42C4
4
Tc42C5
5
Tc42C6
6
Tc42C7
7
Tc42C8
8
Tc42C99
Tc42C10
10
Tc42C11
11
Tc42C12
12

X
C,
N(C)/
at.%
N(Tc)
0
0
0,023810,047619
0,047619
0,071429
0,071429
0,095238
0,119048
0,142857 12.5
0,166667 14
0,190476
0,214286
0,238095 20
0,261905
0,285714

C,
wt.%
0

1.415
1.98

2.94

y(x)

y-y(0)

1,13471,1402
1,1313
1,1323
1,14971,146
1,13491,1301
1,1254
1,1382
1,119
1,1255
1,1294
1,1367
1,109900,0055–0,0034–0,0024
0,015
0,01130,0002–0,0046–0,0093
0,0035–0,0157–0,0092–0,0053
0,002–0,0248

Poster presentation at “Atalante-2004”, Nimes, May 2004,
France, pp. 510 (2004).
(7) K. E. German, A. F. Kuzina, and V. I., Spitsyn. Proc. Russ.
Acad. Sci. 297/2, 381 (1987).
(8) V. N. Gerasimov, S. V. Kryutchkov, K. E. German, V. M.
Kulakov, and A. F. Kuzina, X-ray photoelectron study ofstructure of technetium compounds. In: Technetium and rhenium in chemistry and nuclear medicine. V.3. eds. M.
Nicolini, G. Bandoly, and U. Mazzi, New York: Raven Press,
1990. pp. 231-252.
(9) J. A. Rard, M. H. Rand, G. Andregg, and H. Wanner,
Chemical Thermodynamics, Vol. 3. Chemical Thermodynamics of Technetium (M. C. A. Sandino and E. Östhols,eds.), OECD Nuclear Energy Agency, Data Bank, Issy-lesMoulineaux, France 1999. 567 p.
(10) V. P. Tarasov, Yu. B. Muravlev, and K. E. Guerman, J.
Phys. Condensed Matter, 13, 1 (2001).