Cryogenic pump employing tin—gallium alloys and methods of use
09567988 · 2017-02-14
Assignee
Inventors
Cpc classification
F04B39/06
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25B2309/003
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F04B53/08
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F04B37/08
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25B2309/1415
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
F25B9/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F04B39/06
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F04B37/08
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25B9/14
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
A cryogenic refrigerator includes a regenerative heat exchanger material in thermal contact with a working gas including a tin-antimony (SnSb) alloy or a tin-gallium (SnGa) alloy in at least one cooling stage. The regenerative heat exchanger material can include an SnSb-M alloy, with M including at least one element selected from the group consisting of Bi, Ag, Ge, Cu, La, Mg, Mn, Nd, Ni, Pd, Pt, K, Rh, Sm, Se, S, Y, Fe, In, Al, Ce, Dy, Cd, Ti, Au, P, Pr, Yb and Zn. The cryogenic refrigerator can include a Gifford-McMahon refrigerator, a pulse tube refrigerator, or a Stirling refrigerator. A cryopump includes cryopanels adapted to condense or adsorb gases and a cryogenic refrigerator.
Claims
1. A cryogenic refrigerator comprising at least one cooling stage having a regenerative heat exchanger material in thermal contact with a working gas, including a binary tin-gallium (SnGa) alloy in the at least one cooling stage.
2. The cryogenic refrigerator of claim 1, wherein the cryogenic refrigerator is selected from the group consisting of a Gifford-McMahon cryogenic refrigerator, a pulse tube cryogenic refrigerator, and a Stirling cryogenic refrigerator.
3. The cryogenic refrigerator of claim 1, wherein the SnGa alloy comprises a maximum of 3.9% gallium by weight.
4. The cryogenic refrigerator of claim 1, further including a cryopump that includes at least one cryopanel cooled by the refrigerator and adapted to condense or adsorb gases.
5. The cryogenic refrigerator of claim 1, wherein the at least one cooling stage includes at least two layers of regenerative heat exchanger material.
6. The cryogenic refrigerator of claim 5, wherein at least one layer includes the binary tin-gallium (SnGa) alloy and at least one layer includes at least one rare earth element.
7. The cryogenic refrigerator of claim 5, wherein at least one layer includes the binary tin-gallium (SnGa) alloy and at least one layer includes a rare earth intermetallic compound of one or more rare earth elements with a non-rare earth metal.
8. The cryogenic refrigerator of claim 5, wherein at least one layer includes the binary tin-gallium (SnGa) alloy and at least one layer includes a solid solution alloy of rare earth elements.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
(11) The foregoing will be apparent from the following more particular description of example embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating embodiments of the present invention.
(12) Metallic tin (Sn) is generally non-toxic to humans, even upon uptake of small concentrations for a long period of time, and elemental tin rarely affects human health. As such, tin is an environmentally sensible substitute for lead as a regenerative heat exchanger material applied to cryogenic refrigerators in cryopumps, without significantly compromising volumetric heat capacity as shown in
(13) Tin has two allotropes at normal pressure and temperature: gray alpha ()-tin and white beta ()-tin. Below 13.2 C. at equilibrium, it exists as -tin, which has a cubic crystal structure similar to silicon and germanium. Gray tin has poor metallic properties; it is a dull-gray brittle material. When warmed above 13.2 C. at equilibrium, tin changes into white or -tin, which is a ductile metal with a tetragonal structure. Alpha tin can cause undesirable effects in applications where the ductile properties of tin are important and the transformation results in powdering of the transformed material because of the stresses that result from the volume change associated with the transformation. The transformation of -tin to -tin also occurs slowly when held for a long time below 13.2 C. Incubation times for the formation of -tin can range from months to more than a year. The transformation involves an incubation time in which the alpha phase nucleates at the surface, and a growth phase in which the alpha phase grows into the beta phase over time. The result can be a metallic surface of white tin that becomes covered with a gray powder which is easily rubbed off. This process is known as tin disease or tin pest.
(14) Regenerative heat exchanger materials made of gray or alpha tin are unsuited to be applied in cryogenic cycles, because the low temperature surfaces of cryopumps operate in the range of 4 to 70 K (269 C. to 203 C.) and cycle between room temperature and the cold operating range for regular maintenance and regeneration. The transformation to gray tin is prevented by the addition of antimony (Sb), in sufficient quantity, forming an alloy of tin and antimony. Tin alloys containing one or more of lead and bismuth in sufficient quantities or in combination resulting in sufficient quantities will also eliminate the transformation to -tin. The inclusion of additional elements to enhance properties such as volumetric heat capacity and ductility and minimize thermal conductivity may be included as long as the minimum amount of the inhibiting element is included in the alloy. These alloying elements include but are not limited to: In, Ag, Au, Cd, Ti, Ni, Bi, Ge, Cu, Mg, Mn, Pd, Pt, K, Rh, Se, S, Y, Fe, Al, P, Yb, Zn, and the rare-earth elements.
(15) As such, in certain embodiments of the present invention, the regenerative heat exchanger material for operating a cryogenic refrigerator includes tin-antimony (SnSb) alloy. The regenerative heat exchanger material can generally comprise a plurality of phases, each having a different composition ratio and impurity phases such as oxide and carbide.
(16) In one embodiment, the SnSb alloy can include up to the maximum solid solubility of about 9.6% Sb by weight with a minimum concentration of about 0.5% Sb by weight. Compositions can include up to about 43% Sb by weight.
(17) In certain other embodiments, the regenerative heat exchanger material for operating a cryogenic refrigerator includes a tin-gallium (SnGa) alloy. In one embodiment, the SnGa alloy can include up to the maximum solid solubility of about 3.9% Ga by weight.
(18) In certain embodiments, the regenerative heat exchanger material can be a ternary alloy following the general formula SnSb-M, wherein M is an element selected from the group consisting of Bi, Ag, Ge, Cu, La, Mg, Mn, Nd, Ni, Pd, Pt, K, Rh, Sm, Se, S, Y, Fe, In, Al, Ce, Dy, Cd, Ti, Au, P, Pr, Yb, Er, Ho, Gd, and Zn. In certain embodiments, the SnSb-M alloy material can include from about 0.01% to about 40% of M by weight, from about 0.1% to about 43% of Sb by weight, and from about 50% to about 99.5% of Sn by weight.
(19) Preferably, the regenerative heat exchanger materials of the present invention are comprised of spheres having substantially uniform diameters, in order to provide for minimization of pressure drop along the flow direction of the operating medium (refrigerant), such as helium (He) gas, in a cold-accumulating unit packed with the regenerative heat exchanger material, and in order to increase the heat exchange efficiency between the operating medium and the regenerative heat exchanger material, and to maintain a constant rate of heat exchange within the cold-accumulating unit.
(20) The size of the regenerative heat exchanger material is a factor that has a large influence upon the cooling functions and the heat transfer characteristics of the refrigerator. In one embodiment, the diameter range of the substantially spherical regenerative heat exchanger material is in a range of between about 0.01 mm and about 3 mm.
(21) In an additional embodiment shown in
(22) The cryogenic refrigerator of the present invention is constructed so as to comprise a plurality of cooling stages and alloy materials filled in at least part of a regenerative heat exchanger at a final cooling stage of the refrigerator. For example, in the case of a two-stage expansion type refrigerator, the regenerative heat exchanger material of this invention is filled in a low-temperature end of the regenerator disposed at a second cooling stage. In the case of a three-stage expansion type refrigerator, the regenerative heat exchanger material of this invention is filled in a low-temperature end of a cold-accumulating unit disposed at a third stage. On the other hand, the cold-accumulating units of the other two stages of the three-stage refrigerator, which operate at successively higher temperatures than the third stage, optimally can be filled with other regenerator materials having a high volumetric specific heat at the operating temperature of the particular cold-accumulating unit. The three-stage refrigerator may also contain the material of this invention in portions of the second and/or third stages depending on the operating temperatures of the stages and the heat capacity needed to provide the required cooling. The regenerative heat exchanger material of this invention may be used similarly in systems with more than three stages.
(23) Cryogenic refrigerators of the invention include Gifford-McMahon type cryogenic refrigerators, pulse tube cryogenic refrigerators, and Stirling type cryogenic refrigerators. One embodiment of a Gifford-McMahon cryogenic refrigerator of the invention is shown in
(24) First stage displacer 110 accommodates first stage regenerative heat exchanger material 150. In one embodiment, first stage regenerative heat exchanger material 150 can include copper or stainless steel mesh or an equivalent thereof.
(25) In second stage displacer 115, the low temperature side contains second stage regenerative heat exchanger material 170 made of a regenerative heat exchanger material of this invention for extremely low temperature. In certain embodiments of the present invention, the regenerative heat exchanger material for operating a cryogenic refrigerator includes tin-antimony (SnSb) alloy. In certain other embodiments of the present invention, the regenerative heat exchanger material can be a ternary alloy following the general formula SnSb-M, wherein M is an element selected from the group consisting of Bi, Ag, Ge, Cu, La, Mg, Mn, Nd, Ni, Pd, Pt, K, Rh, Sm, Se, S, Y, Fe, In, Al, Ce, Dy, Au, Cd, Ti, P, Pr, Yb and Zn. Second stage regenerative heat exchanger material 170 is contained within second stage displacer 115 by screens or the like. In certain embodiments, first stage regenerative heat exchanger material 150 and second stage regenerative heat exchanger material 170 can include at least two layers of materials, with various volumetric heat capacities as appropriate to the temperature at the respective location in the regenerator.
(26) First expansion chamber 180 is provided between first stage displacer 110 and second stage displacer 115. Second expansion chamber 185 is provided below second stage displacer 115. First stage cold station 160 is provided around first expansion chamber 180 and, further, second stage cold station 190 which is colder than first stage cold station 160 is provided around second expansion chamber 185. Optional heating sources 195 and 196 can be provided in contact with second stage cold station 190 and first stage cold station 160, respectively, to warm the second and first stages during operation and regular maintenance. Second stage cold station 190 has an operating temperature of about 10 K to about 25 K, and therefore it is a vacuum pumping surface for gases that condense at very low temperatures or are adsorbed by other materials at these cold temperatures. In one embodiment, there is no barrier between the helium gas and high thermal conductivity second stage cold station 190 so that there is direct thermal contact between the helium gas and second stage cold station 190. In another embodiment, either or both first stage cold station 160 and second stage cold station 190 include copper for a greater degree of thermal contact between the helium gas and the respective cold stations.
(27) The flow of working gas refrigerant in the cryogenic refrigerator of a cryopump is cyclic. In the most basic form of a Gifford-McMahon cryogenic refrigerator, shown in
(28) To produce the low temperatures required for cryopump uses, the incoming gas must be cooled before expansion. The regenerator extracts heat from the incoming gas, stores it, and then releases it to the exhaust stream. A regenerator is a reversing-flow heat exchanger through which the helium passes alternately in either direction. The regenerator comprises a material of high surface area, high specific heat, and low thermal conductivity. Thus, the regenerator will accept heat from the helium if the helium's temperature is higher. If the helium's temperature is lower, the regenerator will release heat to the helium.
(29) Further, a second stage of refrigeration can be added, as shown in
(30) One embodiment of a cryopump that includes a Gifford-McMahon cryogenic refrigerator is shown in
(31) In certain embodiments of a Gifford-McMahon cryopump, the first stage regenerative heat exchanger material (not shown in
(32) In certain embodiments of a Gifford-McMahon cryopump, there is no barrier between the working gas, for example, helium, and high thermal conductivity second stage cold station 190 so that there is direct thermal contact between the helium gas and second stage cold station 190. In another embodiment, either or both first stage cold station 160 and second stage cold station 190 include copper for a greater degree of thermal contact between the helium gas and the respective cold stations.
(33) A cryopump can include a pulse tube refrigerator. Pulse tube refrigerators are regenerative refrigerators in which a pressure wave travels back and forth through a buffer tank, a pulse tube, and a section containing the regenerative heat exchanger material. The pressure wave creates an oscillating gas column, called a gas piston, that functions as a compressible displacer to move the working gas back and forth through the regenerative heat exchanger material. In this process, one end of the pulse tube is cooled, creating a cold station region, and the other end of the pulse tube is heated, creating a hot station region, where heat is dissipated away from the refrigerator. The pressure wave can be created by a compressor connected to the pulse tube refrigerator by high and low pressure gas lines, or by oscillators such as acoustic sources and pistons, and therefore a pulse tube refrigerator has no moving parts at the cold end. Some pulse tube refrigerators contain an orifice between the pulse tube and the buffer tank to act as a flow resistance to enable proper phasing of the gas motion and pressure wave. Pulse tube refrigerators can be single stage or can contain multiple stages. The basic operation of a pulse tube refrigerator is described in Development of the Pulse Tube Refrigerator as an Efficient and Reliable Cryocooler, R. Radebaugh, Proceedings of the Institute of Refrigeration, Vol. 96 (London, 1999/2000), the entire teachings of which are incorporated herein by reference.
(34) One embodiment of a cryopump that includes a pulse tube cryogenic refrigerator is shown in
(35) In one embodiment of the cryopump shown in
(36) In certain embodiments of a pulse tube cryopump, there is no barrier between the working gas, for example, helium, and high thermal conductivity second stage cold station 560 so that there is direct thermal contact between the helium gas and second stage cold station 560. In another embodiment, either or both first stage cold station 460 and second stage cold station 560 include copper for a greater degree of thermal contact between the helium gas and the respective cold stations.
(37) A cryopump can include a Stirling cryogenic refrigerator. One embodiment of a two-stage Stirling cryogenic refrigerator is shown in
(38) In certain embodiments of a Stirling cryogenic refrigerator, first stage regenerative heat exchanger material 150 and second stage regenerative heat exchanger material 170 can include at least two layers as described above, with various volumetric heat capacities as appropriate to the temperature at the respective location in the regenerator. First stage displacer 630 accommodates first stage regenerative heat exchanger material 150. In one embodiment, first stage regenerative heat exchanger material 150 can include copper or stainless steel mesh or an equivalent thereof.
(39) In second stage displacer 640, the low temperature side contains second stage regenerative heat exchanger material 170 made of a regenerative heat exchanger material of this invention for extremely low temperature that includes tin-antimony (SnSb) alloy.
(40) First stage cold station 160 is provided at the end of first stage displacer 630 distal from pressure wave source 610, and, further, second stage cold station 190 which is colder than first stage cold station 160 is provided at the end of second stage displacer 640 distal from first stage cold station 160. Second stage cold station 190 has an operating temperature of about 10 K to about 25 K, and therefore it is a vacuum pumping surface for gases that condense at very low temperature or are adsorbed by other materials at these cold temperatures. Heat is extracted from first stage thermal load 112 and second stage thermal load 117. In another embodiment of a Stirling cryogenic refrigerator, pressure wave source 610 can be a piston or an acoustic source. In yet another embodiment of a Stirling cryogenic refrigerator, shown in
(41) One embodiment of a cryopump that includes a two-stage Stirling cryogenic refrigerator is shown in
EXEMPLIFICATION
(42) Regenerative heat exchanger materials in the form of 0.28 mm diameter round shot with a composition of 95% Sn by weight and 5% Sb by weight were tested in a standard two stage Gifford-McMahon refrigerator. The SnSb regenerative materials of uniform size and composition were contained in heat exchanger 170 of the second stage displacer 115 of Gifford-McMahon refrigerator 100, shown in
(43) The teachings of all patents, published applications and references cited herein are incorporated by reference in their entirety.
EQUIVALENTS
(44) While this invention has been particularly shown and described with references to example embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.