The half Heusler system Ti1+xFe1.33−xSb-TiCoSb with Sb/Sn substitution: phase relations, crystal structures and thermoelectric properties
Investigations of phase relations in the ternary system Ti-Fe-Sb show that the single-phase region of the Heusler phase is significantly shifted from stoichiometric TiFeSb (reported previously in the literature) to the Fe-rich composition TiFe 1.33 Sb. This compound also exhibits Fe/Ti substitution...
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Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 47; no. 3; pp. 879 - 897 |
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Main Authors | , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
Cambridge
Royal Society of Chemistry
15.01.2018
|
Subjects | |
Online Access | Get full text |
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Summary: | Investigations of phase relations in the ternary system Ti-Fe-Sb show that the single-phase region of the Heusler phase is significantly shifted from stoichiometric TiFeSb (reported previously in the literature) to the Fe-rich composition TiFe
1.33
Sb. This compound also exhibits Fe/Ti substitution according to Ti
1+
x
Fe
1.33−
x
Sb (−0.17 ≤
x
≤ 0.25 at 800 °C). Its stability, crystal symmetry and site preference were established by using X-ray powder techniques and were backed by DFT calculations. The
ab initio
modeling revealed TiFe
1.375
Sb to be the most stable composition and established the mechanisms behind Fe/Ti substitution for the region Ti
1+
x
Fe
1.33−
x
Sb, and of the Fe/Co substitution within the isopleth TiFe
1.33
Sb-TiCoSb. The calculated residual resistivity of Ti
1+
x
Fe
1.33−
x
Sb, as well as of the isopleths TiFe
1.33
Sb-TiCoSb, TiFe
0.665
Co
0.5
Sb-TiCoSb
0.75
Sn
0.25
and TiFe
0.33
Co
0.75
Sb-TiCoSb
0.75
Sn
0.25
, are in a good correlation with the experimental data. From magnetic measurements and
57
Fe Mössbauer spectrometry, a paramagnetic behavior down to 4.2 K was observed for TiFe
1.33
Sb, with a paramagnetic Curie-Weiss temperature of −8 K and an effective moment of 1.11
μ
B
per Fe. Thermoelectric (TE) properties were obtained for the four isopleths Ti
1+
x
Fe
1.33−
x
Sb, TiFe
1.33
Sb-TiCoSb, TiFe
0.665
Co
0.5
Sb-TiCoSb
0.75
Sn
0.25
and TiFe
0.29
Co
0.78
Sb-TiCoSb
0.75
Sn
0.25
by measurements of electrical resistivity (
ρ
), Seebeck coefficient (
S
) and thermal conductivity (
λ
) at temperatures from 300 K to 823 K allowing the calculation of the dimensionless figure of merit (
ZT
). Although p-type Ti
1+
x
Fe
1.33−
x
Sb indicates a semi-conducting behavior for the Fe rich composition (
x
= −0.133), the conductivity changes to a metallic type with increasing Ti content. The highest
ZT
= 0.3 at 800 K was found for the composition TiFe
1.33
Sb. The TE performance also increases with Fe/Co substitution and reaches
ZT
= 0.42 for TiCo
0.5
Fe
0.665
Sb. No further increase of the TE performance was observed for the Sb/Sn substituted compounds within the sections TiFe
0.665
Co
0.5
Sb-TiCoSb
0.75
Sn
0.25
and TiFe
0.33
Co
0.75
Sb-TiCoSb
0.75
Sn
0.25
. However,
ZT
-values could be enhanced by about 12%
via
the optimization of the preparation route (ball-mill conditions and heat treatments).
Phase equilibria for Heusler Phase Ti
1+
x
Fe
1.33−
x
Sb at 800 °C and calculated isosurfaces (
= 0.42) of the electron localization function in TiFe
1.25
Sb. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c7dt03787b |