International
Tables for
Crystallography
Volume D
Physical properties of crystals
Edited by A. Authier

International Tables for Crystallography (2006). Vol. D. ch. 1.4, pp. 101-102

Section 1.4.3.1. General remarks

H. Küppersa*

a Institut für Geowissenshaften, Universität Kiel, Olshausenstrasse 40, D-24098 Kiel, Germany
Correspondence e-mail: [email protected]

1.4.3.1. General remarks

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Although the strain tensor Mathematical symbol and the thermal expansion tensor Mathematical symbol in general contain components with Mathematical symbol (shear strains), in practice only longitudinal effects, i.e. relative length changes Mathematical symbol with temperature changes ΔT, are measured along different directions and the results are later transformed to a common coordinate system. Diffraction methods directly yield this ratio Mathematical symbol. Other measuring techniques require separate measurements of Δl and l. The error in the measurement of l can usually be neglected. Thus, the accuracies of Δl and ΔT limit the accuracy of thermal expansion coefficients. The temperature interval ΔT is determined by two measurements of temperatures Mathematical symbol, with Mathematical symbol. To increase the accuracy of the difference ΔT, this interval should be large. The measured thermal expansion Mathematical symbol is usually assigned to a temperature at the midpoint of the temperature interval, Mathematical symbol. This procedure is only justified if thermal expansion does not depend on temperature.

Since, in fact, thermal expansion depends on temperature, in principle, smaller intervals should be chosen, which, in turn, enlarge the error of ΔT. Here, a compromise has to be made. Sometimes, after completion of a first run and after reviewing the preliminary course of Mathematical symbol, it is necessary to repeat some measurements using smaller temperature intervals in temperature ranges with large curvatures.

The more-or-less curved course of Mathematical symbol is usually fitted by polynomials in powers of temperature. Here, those T terms should be selected that are physically meaningful in the particular temperature range. For the low-temperature behaviour of a metal, a polynomial of type Mathematical symbol should be chosen. For minerals at higher temperatures, a polynomial Mathematical symbol is used (Saxena & Shen, 1992link to reference).

Temperature is usually measured by thermocouples and, in the cases of optical or electrical measurements (Sections 1.4.3.3link to section and 1.4.3.4link to section) and at low temperatures also by platinum resistance thermometers. Above 1100 K, optical pyrometers can be used.

In order to measure the thermal expansion of a crystal, at least as many independent measurements are necessary as the tensor has independent components (fourth column in Table 1.4.1.1link to table). It is advisable, however, to carry out more measurements than are necessary. In this case (of redundancy), a `best' set of tensor components is to be determined by least-squares methods as described below.

Let us assume the most general case of a triclinic crystal, where Mathematical symbol independent measurements of thermal expansions Mathematical symbol Mathematical symbol were performed along m different directions with direction cosines Mathematical symbol Mathematical symbol with respect to the chosen coordinate system. Each measurement Mathematical symbol is related to the six unknown tensor components Mathematical symbol (to be determined) by Mathematical equationIf the Mathematical symbol are replaced by Mathematical symbol Mathematical symbol, using Voigt's one-index notation (Section 1.1.4.10.2[link] ), then Mathematical symbol represents an overdetermined inhomogeneous system of m linear equations for the six unknowns Mathematical symbol. The coefficients Mathematical symbol, forming an Mathematical symbol matrix, are products containing direction cosines according to (1.4.3.1)link to equation. The solution is obtained after several matrix calculations which are indicated by the formula (Nye, 1985link to reference) Mathematical equationwhere a superscript `t' means transposed.

Instead of determining the tensor components of a triclinic or monoclinic crystal in a direct way, as outlined above, it is also possible to determine first the temperature change of the crystallographic unit cell and then, by formulae given e.g. by Schlenker et al. (1978)link to reference, to deduce the tensor components Mathematical symbol. The direct approach is recommended, however, for reasons of the propagation of errors (Jessen & Küppers, 1991link to reference).

The experimental techniques of measuring relative length changes Mathematical symbol that are most widely used include diffraction, optical interferometry, pushrod dilatometry and electrical capacitance methods. If the specimens available are very small and/or irregular in shape, only diffraction methods can be used. The other methods require single-crystal parallelepipedal samples with at least 5 mm side lengths.

References

First citation Jessen, S. M. & Küppers, H. (1991). The precision of thermal-expansion tensors of triclinic and monoclinic crystals. J. Appl. Cryst. 24, 239–242.Google Scholar
First citation Nye, J. F. (1985). Physical properties of crystals. Oxford: Clarendon Press.Google Scholar
First citation Saxena, S. K. & Shen, G. (1992). Assessed data on heat capacity, thermal expansion, and compressibility of some oxides and silicates. J. Geophys. Res. 97, 19813–19825.Google Scholar
First citation Schlenker, J. L., Gibbs, G. V. & Boisen, M. B. (1978). Strain-tensor components expressed in terms of lattice parameters. Acta Cryst. A34, 52–54.Google Scholar








































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