A knowledge of the properties and behavior of materials used in any cryogenic system is essential for proper design considerations. Often the choice of materials for the construction of cryogenic equipment will be dictated by other considerations besides mechanical properties as, for example, thermal conductivity (heat transfer along a structural member), thermal expansivity (expansion and contraction during cycling between ambient and low temperatures), and density (mass of the system). Since properties at low temperatures are often significantly different from those at ambient temperature, there is no substitute for test data on a truly representative sample specimen when designing for the limit of effectiveness of a cryogenic material or structure. For example, some metals including elements, intermetal-lic compounds and alloys exhibit the phenomenon of superconductivity at very low temperatures. The properties that are affected when a material becomes superconducting include specific heat, thermal conductivity, electrical resistance, magnetic permeability, and thermoelectric effect. As a result, the use of superconducting metals in the construction of equipment for temperatures lower than 10 K needs to be evaluated carefully. (High temperature superconductors because of their brittle ceramic structure are presently not considered as construction materials.)
Structural Properties at Low Temperatures It is most convenient to classify metals by their lattice symmetry for low temperature mechanical properties considerations. The face-centered-cubic (fcc) metals and their alloys are most often used in the construction of cryogenic equipment. Al, Cu Ni, their alloys, and the austenitic stainless steels of the 18-8 type are fcc and do not exhibit an impact ductile-to-brittle transition at low temperatures. As a general rule, the mechanical properties of these metals with the exception of 2024-T4 aluminum, improve as the temperature is reduced. Since annealing of these metals and alloys can affect both the ultimate and yield strengths, care must be exercised under these conditions.
The body-centered-cubic (bcc) metals and alloys are normally classified as undesirable for low temperature construction. This class includes Fe, the martensitic steels (low carbon and the 400-series stainless steels), Mo, and Nb. If not brittle at room temperature, these materials exhibit a ductile-to-brittle transition at low temperatures. Cold working of some steels, in particular, can induce the austenite-to-martensite transition.
The hexagonal-close-packed (hcp) metals generally exhibit mechanical properties intermediate between those of the fcc and bcc metals. For example Zn encounters a ductile-to-brittle transition whereas Zr and pure Ti do not. The latter and their alloys with a hcp structure remain reasonably ductile at low temperatures and have been used for many applications where weight reduction and reduced heat leakage through the material have been important. However, small impurities of O, N, H, and C can have a detrimental effect on the low temperature ductility properties of Ti and its alloys.
Plastics increase in strength as the temperature is decreased, but this is also accompanied by a rapid decrease in elongation in a tensile test and a decrease in impact resistance. Teflon and glass-reinforced plastics retain appreciable impact resistance as the temperature is lowered. The glass-reinforced plastics also have high strength-to-weight and strength-to-thermal conductivity ratios. Allelastomers, on the other hand, become brittle at low temperatures. Nevertheless, many of these materials including rubber, Mylar, and nylon can be used for static seal gaskets provided they are highly compressed at room temperature prior to cooling.
The strength of glass under constant loading also increases with decrease in temperature. Since failure occurs at a lower stress when the glass surface contains surface defects, the strength can be improved by tempering the surface.
Thermal Properties at Low Temperatures For solids, the Debye model developed with the aid of statistical mechanics and quantum theory gives a satisfactory representation of the specific heat with temperature. Procedures for calculating values of 0D, the Debye characteristic temperature, using either elastic constants, the compressibility, the melting point, or the temperature dependence of the expansion coefficient are outlined by Barron (Cryogenic Systems, 2d ed., Oxford University Press, 1985, pp 24-29).
Adequate prediction of the thermal conductivity for pure metals can be made by means of the Wiedeman-Franz law which states that the ratio of the thermal conductivity to the product of the electrical conductivity and the absolute temperature is a constant. This ratio for high-conductivity metals extrapolates essentially to the Sommerfeld value of 2.449 X 10"8 W £2/K2 at 0 K, but falls considerably below it at higher temperatures. High-purity aluminum and copper exhibit peaks in thermal conductivity between 20 to 50 K, but these peaks are rapidly suppressed with increased impurity levels and cold work of the metal. Some metals including Monel, Inconel, stainless steel, and structural and aluminum alloys show a steady decrease in thermal conductivity with a decrease in temperature.
All cryogenic liquids except hydrogen and helium have thermal conductivities that increase as the temperature is decreased. For these two exceptions, the thermal conductivity decreases with a decrease in temperature. The kinetic theory of gases correctly predicts the decrease in thermal conductivity of all gases when the temperature is lowered.
The expansion coefficient of a solid can be estimated with the aid of an approximate thermodynamic equation of state for solids which equates the thermal expansion coefficient P with the quantity gCv p/B where g is the Gruneisen dimensionless ratio, Cv is the specific heat of the solid, p is the density of the material, and B is the bulk modulus. For fcc metals the average value of the Gruneisen constant is near 2.3. However, there is a tendency for this constant to increase with atomic number.
Electrical Properties at Low Temperatures The electrical resistivity of most pure metallic elements at ambient and moderately low temperatures is approximately proportional to the absolute temperature. At very low temperatures, however, the resistivity (with the exception of superconductors) approaches a residual value almost independent of temperature. Alloys, on the other hand, have resistivities much higher than those of their constituent elements and resistance-temperature coefficients that are quite low. The electrical resistivity of alloys as a consequence is largely independent of temperature and may often be of the same magnitude as the room temperature value.
Superconductivity The physical state in which all resistance to the flow of direct-current electricity disappears is defined as superconductivity. The Bardeen-Cooper-Schriefer (BCS) theory has been reasonably successful in accounting for most of the basic features observed of the superconducting state for low-temperature .superconductors (LTS) operating below 23 K. The advent of the ceramic high-temperature .superconductors (HTS) by Bednorz and Miller (Z. Phys. B64, 189, 1989) has called for modifications to existing theories which have not been finalized to date. The massive interest in the new superconductors that can be cooled with liquid nitrogen is just now beginning to make its way into new applications.
Three important characteristics of the superconducting state are the critical temperature, the critical magnetic field, and the critical current. These parameters can be varied by using different materials or giving them special metallurgical treatments.
The alloy niobium titanium (NbTi) and the intermetallic compound of niobium and tin (Nb3 Sn) are the most technologically advanced LTS materials presently available. Even though NbTi has a lower critical field and critical current density, it is often selected because its metallurgical properties favor convenient wire fabrication. In contrast, Nb3Sn is a very brittle material and requires wire fabrication under very well-defined temperature conditions.
There are presently four families of high-temperature superconductors under investigation for practical magnet applications. Table 11-25 shows that all HTS are copper oxide ceramics even though the oxygen content may vary. However, this variation generally has little effect on the physical properties of importance to superconductivity.
The most widely used development in HTS wire production is the powder-in-tube procedure with BSCCO ceramic materials. In this procedure very fine HTS powder, placed inside of a hollow silver tube, is fused as the tube length is mechanically increased to form a wire. Very high magnetic fields with this wire have been reported at 4 K; however, the performance degrades substantially above 20 to 30 K.
HTS materials, because of their ceramic nature, are quite brittle. This has introduced problems relative to the winding of superconducting magnets. One solution is to first wind the magnet with the powder-in-tube wire before the ceramic powder has been bonded and then heat treat the desired configuration to form the final product. Another solution is to form the superconductor into such fine fila-
Critical Tc, K
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