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Thermodynamic properties and ordering in PdAl

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Abstract

The activity of aluminum in the Pd-Al system was determined by an isopiestic method from 30 to 80 at. pct Al between 1090° and 1490°K. It shows a strong negative deviation from ideality, with a decrease in activity of aluminum of four orders of magnitude around the stoichiometric composition of PdAl. The defect structure in the CsCl-structure PdAl compound has been determined by lattice parameter measurements. Equations were derived relating the degree of intrinsic disorder (α) to the shape of the activity curve. Excellent agreement between the calculated curve and the activity data was obtained for anα = 2.5 × 10−4. The results from this investigation and from previous studies indicate that the degree of intrinsic disorder in the equiatomic transition metal-aluminum compounds is controlled by electronic effects.

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Abbreviations

α :

degree of intrinsic disorder

N s :

total number of lattice sites

N s /Pd,N s /Al :

number of palladium sites, number of aluminum sites

N Pd Pd,N Al Al :

number of palladium atoms on palladium sites, number of aluminum atoms on aluminum sites

N V /Pd,N V /Al :

number of palladium vacancies, number of aluminum vacancies

N A /Pd,N A /Al :

number of palladium atoms on aluminum sites, number of aluminum atoms on palladium sites

δx Al :

mole fraction deviation from the stoichiometric composition

λAl, λPd :

absolute activity of aluminum, absolute activity of palladium

λ *Al :

absolute activity of aluminum at the stoichiometric composition

a Al :

activity of aluminum

Q 0 :

partition function for the perfectly ordered stoichiometric composition

K Pd,K Al :

terms independent of the number of defects which contain the acoustical, magnetic and electronic contribution to the GPF

T(N) :

arbitrary term of the GPF

E A /Pd,E V /Pd :

energy of formation of a palladium antistructure defect, energy of formation of a palladium vacancy

V Pd,V Al :

vacancies of palladium, vacancies of aluminum

PdPd, AlAl :

palladium on palladium sites, aluminum on aluminum sites

AlPd, PdAl :

aluminum on palladium sites palladium on aluminum sites

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Authors and Affiliations

  1. RCA Research Laboratories, Princeton, N.J.

    M. Ettenberg

  2. Department of Inorganic Chemistry, University of Vienna, Vienna, Austria

    K. L. Komarek (Chairman)

  3. Department of Mechanical Engineering, California State College at Long Beach, Long Beach, Calif.

    E. Miller (Associate Professor)

Authors
  1. M. Ettenberg
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  2. K. L. Komarek
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  3. E. Miller
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Additional information

Formely Department of Metallurgy and Materials Sciences, New York University, New York, N. Y.

Formerly Department of Metallurgy and Materials Sciences, New York University

Formerly Department of Metallurgy and Materials Sciences, New York University

This paper is based on a Thesis submitted by M. ETTENBERG to the Graduate Division, School of Engineering and Science, New York University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science.

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Ettenberg, M., Komarek, K.L. & Miller, E. Thermodynamic properties and ordering in PdAl. Metall Trans 2, 1173–1181 (1971). https://doi.org/10.1007/BF02664249

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