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Cryogenics
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In physics, cryogenics is the production and behaviour of materials at very low temperatures.
The 13th International Institute of Refrigeration's (IIR) International Congress of Refrigeration (held in Washington, DC in 1971) endorsed a universal definition of "cryogenics" and "cryogenic" by accepting a threshold of 120 K (−153 °C) to distinguish these terms from conventional refrigeration.[1][2][3][4] This is a logical dividing line, since the normal boiling points of the so-called permanent gases (such as helium, hydrogen, neon, nitrogen, oxygen, and normal air) lie below 120 K, while the Freon refrigerants, hydrocarbons, and other common refrigerants have boiling points above 120 K.[5][6]
Discovery of superconducting materials with critical temperatures significantly above the boiling point of nitrogen has provided new interest in reliable, low-cost methods of producing high-temperature cryogenic refrigeration. The term "high temperature cryogenic" describes temperatures ranging from above the boiling point of liquid nitrogen, −195.79 °C (77.36 K; −320.42 °F), up to −50 °C (223 K; −58 °F).[7] The discovery of superconductive properties is first attributed to Heike Kamerlingh Onnes on July 10, 1908, after they were able to reach a temperature of 2 K. These first superconductive properties were observed in mercury at a temperature of 4.2 K.[8]
Cryogenicists use the Kelvin or Rankine temperature scale, both of which measure from absolute zero, rather than more usual scales such as Celsius which measures from the freezing point of water at sea level[9][10] or Fahrenheit which measures from the freezing point of a particular brine solution at sea level.[11][12]
Definitions and distinctions
[edit]Cryogenics
[edit]The branches of engineering that involve the study of very low temperatures (ultra low temperature i.e. below 123 K), how to produce them, and how materials behave at those temperatures.
Cryobiology
[edit]The branch of biology involving the study of the effects of low temperatures on organisms (most often for the purpose of achieving cryopreservation). Other applications include Lyophilization (freeze-drying) of pharmaceutical[13] components and medicine.
Cryoconservation of animal genetic resources
[edit]The conservation of genetic material with the intention of conserving a breed. The conservation of genetic material is not limited to non-humans. Many services provide genetic storage or the preservation of stem cells at birth. They may be used to study the generation of cell lines or for stem-cell therapy.[14]
Cryosurgery
[edit]The branch of surgery applying cryogenic temperatures to destroy and kill tissue, e.g. cancer cells. Commonly referred to as Cryoablation.[15]
Cryoelectronics
[edit]The study of electronic phenomena at cryogenic temperatures. Examples include superconductivity and variable-range hopping.
Cryonics
[edit]Cryopreserving humans and animals with the intention of future revival. "Cryogenics" is sometimes erroneously used to mean "Cryonics" in popular culture and the press.[16]
Etymology
[edit]The word cryogenics stems from Greek κρύος (cryos) – "cold" + γενής (genis) – "generating".
Cryogenic fluids
[edit]
Cryogenic fluids with their boiling point in Kelvin[17] and degree Celsius.
| Fluid | Boiling point (K) | Boiling point (°C) |
|---|---|---|
| Helium-3 | 3.19 | −269.96 |
| Helium-4 | 4.214 | −268.936 |
| Hydrogen | 20.27 | −252.88 |
| Neon | 27.09 | −246.06 |
| Nitrogen | 77.09 | −196.06 |
| Air | 78.8 | −194.35 |
| Fluorine | 85.24 | −187.91 |
| Argon | 87.24 | −185.91 |
| Oxygen | 90.18 | −182.97 |
| Methane | 111.7 | −161.45 |
| Krypton | 119.93 | −153.415 |
Industrial applications
[edit]Liquefied gases, such as liquid nitrogen and liquid helium, are used in many cryogenic applications. Liquid nitrogen is the most commonly used element in cryogenics and is legally purchasable around the world. Liquid helium is also commonly used and allows for the lowest attainable temperatures to be reached.
These liquids may be stored in Dewar flasks, which are double-walled containers with a high vacuum between the walls to reduce heat transfer into the liquid. Typical laboratory Dewar flasks are spherical, made of glass and protected in a metal outer container. Dewar flasks for extremely cold liquids such as liquid helium have another double-walled container filled with liquid nitrogen. Dewar flasks are named after their inventor, James Dewar, the man who first liquefied hydrogen. Thermos bottles are smaller vacuum flasks fitted in a protective casing.
Cryogenic barcode labels are used to mark Dewar flasks containing these liquids, and will not frost over down to −195 degrees Celsius.[18]
Cryogenic transfer pumps are the pumps used on LNG piers to transfer liquefied natural gas from LNG carriers to LNG storage tanks, as are cryogenic valves.
Cryogenic processing
[edit]The field of cryogenics advanced during World War II when scientists found that metals frozen to low temperatures showed more resistance to wear. Based on this theory of cryogenic hardening, the commercial cryogenic processing industry was founded in 1966 by Bill and Ed Busch. With a background in the heat treating industry, the Busch brothers founded a company in Detroit called CryoTech in 1966.[19] Busch originally experimented with the possibility of increasing the life of metal tools to anywhere between 200% and 400% of the original life expectancy using cryogenic tempering instead of heat treating.[20] This evolved in the late 1990s into the treatment of other parts.
Cryogens, such as liquid nitrogen, are further used for specialty chilling and freezing applications. Some chemical reactions, like those used to produce the active ingredients for the popular statin drugs, must occur at low temperatures of approximately −100 °C (−148 °F). Special cryogenic chemical reactors are used to remove reaction heat and provide a low temperature environment. The freezing of foods and biotechnology products, like vaccines, requires nitrogen in blast freezing or immersion freezing systems. Certain soft or elastic materials become hard and brittle at very low temperatures, which makes cryogenic milling (cryomilling) an option for some materials that cannot easily be milled at higher temperatures.
Cryogenic processing is not a substitute for heat treatment, but rather an extension of the heating–quenching–tempering cycle. Normally, when an item is quenched, the final temperature is ambient. The only reason for this is that most heat treaters do not have cooling equipment. There is nothing metallurgically significant about ambient temperature. The cryogenic process continues this action from ambient temperature down to −320 °F (140 °R; 78 K; −196 °C). In most instances the cryogenic cycle is followed by a heat tempering procedure. As all alloys do not have the same chemical constituents, the tempering procedure varies according to the material's chemical composition, thermal history and/or a tool's particular service application.
The entire process takes 3–4 days.
Fuels
[edit]Another use of cryogenics is cryogenic fuels for rockets with liquid hydrogen as the most widely used example, with liquid methane starting to become more prevalent in recent years. Liquid oxygen (LOX) is even more widely used but as an oxidizer, not a fuel. NASA's workhorse Space Shuttle used cryogenic hydrogen/oxygen propellant as its primary means of getting into orbit. LOX is also widely used with RP-1 kerosene, a non-cryogenic hydrocarbon, such as in the rockets built for the Soviet space program by Sergei Korolev.
Russian aircraft manufacturer Tupolev developed a version of its popular design Tu-154 with a cryogenic fuel system, known as the Tu-155. The plane uses a fuel referred to as liquefied natural gas or LNG, and made its first flight in 1989.[21]
Other applications
[edit]
Some applications of cryogenics:
- Nuclear magnetic resonance (NMR) is one of the most common methods to determine the physical and chemical properties of atoms by detecting the radio frequency absorbed and subsequent relaxation of nuclei in a magnetic field. This is one of the most commonly used characterization techniques and has applications in numerous fields. Primarily, the strong magnetic fields are generated by supercooling electromagnets, although there are spectrometers that do not require cryogens. In traditional superconducting solenoids, liquid helium is used to cool the inner coils because it has a boiling point of around 4 K at ambient pressure. Inexpensive metallic superconductors can be used for the coil wiring. So-called high-temperature superconducting compounds can be made to super conduct with the use of liquid nitrogen, which boils at around 77 K.
- Magnetic resonance imaging (MRI) is a complex application of NMR where the geometry of the resonances is deconvoluted and used to image objects by detecting the relaxation of protons that have been perturbed by a radio-frequency pulse in the strong magnetic field. This is most commonly used in health applications.
- Cryogenic electron microscopy (cryoEM) is a popular method in structural biology for elucidating the structures of proteins, cells, and other biological systems. Samples are plunge-frozen into a cryogen such as liquid ethane cooled by liquid nitrogen, and are then kept at liquid nitrogen temperature as they are inserted into an electron microscope for imaging. Electron microscopes are also themselves cooled by liquid nitrogen.
- In large cities, it is difficult to transmit power by overhead cables, so underground cables are used. But underground cables get heated and the resistance of the wire increases, leading to waste of power. Superconductors could be used to increase power throughput, although they would require cryogenic liquids such as nitrogen or helium to cool special alloy-containing cables to increase power transmission. Several feasibility studies have been performed and the field is the subject of an agreement within the International Energy Agency.
- Cryogenic gases are used in transportation and storage of large masses of frozen food. When very large quantities of food must be transported to regions like war zones, earthquake hit regions, etc., they must be stored for a long time, so cryogenic food freezing is used. Cryogenic food freezing is also helpful for large scale food processing industries.
- Many infrared (forward looking infrared) cameras require their detectors to be cryogenically cooled.
- Certain rare blood groups are stored at low temperatures, such as −165°C, at blood banks.
- Cryogenics technology using liquid nitrogen and CO2 has been built into nightclub effect systems to create a chilling effect and white fog that can be illuminated with colored lights.
- Cryogenic cooling is used to cool the tool tip at the time of machining in manufacturing process. It increases the tool life. Oxygen is used to perform several important functions in the steel manufacturing process.
- By freezing an automobile or truck tire in liquid nitrogen, the rubber is made brittle and can be crushed into small particles. These particles can be used again for other items.
- Experimental research on certain physics phenomena, such as spintronics and magnetotransport properties, requires cryogenic temperatures for the effects to be observable.
- Certain vaccines must be stored at cryogenic temperatures. For example, the Pfizer–BioNTech COVID-19 vaccine must be stored at temperatures of −90 to −60 °C (−130 to −76 °F). (See cold chain.)[23]
Production
[edit]Cryogenic cooling of devices and material is usually achieved via the use of liquid nitrogen, liquid helium, or a mechanical cryocooler (which uses high-pressure helium lines). Gifford-McMahon cryocoolers, pulse tube cryocoolers and Stirling cryocoolers are in wide use with selection based on required base temperature and cooling capacity. The most recent development in cryogenics is the use of magnets as regenerators as well as refrigerators. These devices work on the principle known as the magnetocaloric effect.
Detectors
[edit]There are various cryogenic detectors which are used to detect particles.
For cryogenic temperature measurement down to 30 K, Pt100 sensors, a resistance temperature detector (RTD), are used. For temperatures lower than 30 K, it is necessary to use a silicon diode for accuracy.
See also
[edit]References
[edit]- ^ International Dictionary of Refrigeration, http://dictionary.iifiir.org/search.php, Archived 2019-10-01 at the Wayback Machine.
- ^ ASHRAE Terminology, https://www.ashrae.org/technical-resources/free-resources/ashrae-terminology.
- ^ "Cryogenics is usually defined as the science and technology dealing with temperatures less than about 120 K [4, 5], although this review does not adhere to a strict 120 K definition." K. D. Timmerhaus, R. Reed. Cryogenic Engineering: Fifty Years of Progress. Springer Science+Business Media LLC (2007), chapter: 1.2, The Beginning of Cryogenics, p. 7.
- ^ "About Cryogenics".
In terms of the Kelvin scale the cryogenic region is often considered to be that below approximately 120 K (−153 C).
- ^ "DICHLORODIFLUOROMETHANE at Pubchem".
- ^ "PROPANE at Pubchem".
- ^ J. M. Nash, 1991, "Vortex Expansion Devices for High Temperature Cryogenics", Proceedings of the 26th Intersociety Energy Conversion Engineering Conference, Vol. 4, pp. 521–525.
- ^ Radebaugh, R. (2007), Timmerhaus, Klaus D.; Reed, Richard P. (eds.), "Historical Summary of Cryogenic Activity Prior to 1950", Cryogenic Engineering, International Cryogenics Monograph Series, New York, New York: Springer, pp. 3–27, Bibcode:2007cren.book....3R, doi:10.1007/0-387-46896-x_1, ISBN 978-0-387-46896-9.
- ^ Celsius, Anders (1742) "Observationer om twänne beständiga grader på en thermometer" (Observations about two stable degrees on a thermometer), Kungliga Svenska Vetenskapsakademiens Handlingar (Proceedings of the Royal Swedish Academy of Sciences), 3: 171–180 and Fig. 1.
- ^ Don Rittner; Ronald A. Bailey (2005): Encyclopedia of Chemistry. Facts On File, Manhattan, New York City, p. 43.
- ^ Fahrenheit temperature scale, Encyclopædia Britannica Online. 25 September 2015.
- ^ "Fahrenheit: Facts, History & Conversion Formulas". Live Science. Retrieved 2018-02-09.
- ^ Evans, Nicole. "What is Cryobiology?". www.societyforcryobiology.org. Retrieved 2023-11-27.
- ^ Hunt, Charles (April 3, 2011). "Cryopreservation of Human Stem Cells for Clinical Application: A Review". Transfusion Medicine and Hemotherapy. 38 (2): 107–123. doi:10.1159/000326623. PMC 3088734. PMID 21566712.
- ^ "Cryosurgery to Treat Cancer". NCI. June 21, 2021. Retrieved 2023-11-27.
- ^ "Cryonics is NOT the Same as Cryogenics". Cryogenic Society of America. Archived from the original on 2 December 2018. Retrieved 5 March 2013.
- ^ Randall Barron, CRYOGENIC SYSTEMS, McGraw-Hill Book Company.
- ^ Thermal, Timmy. "Cryogenic Labels". MidcomData. Retrieved 11 August 2014.
- ^ Gantz, Carroll (2015). Refrigeration: A History. Jefferson, North Carolina: McFarland & Company, Inc. p. 227. ISBN 978-0-7864-7687-9.
- ^ Zohuri, Bahman (2018). "Chapter 1 - Cryogenic Technologies". Physics of Cryogenics: An Ultralow Temperature Phenomenon. Elsevier. p. 34. doi:10.1016/C2017-0-01796-2. ISBN 978-0-12-814519-7.
- ^ "Tu-155 / Tu-156". www.globalsecurity.org. Retrieved 2023-11-27.
- ^ "ESO Signs Technology Transfer Licence Agreement for Cooling System". Retrieved 11 June 2015.
- ^ "Pfizer–BioNTech COVID-19 Vaccine Vaccination Storage & Dry Ice Safety Handling". Pfizer-BioNTech. Archived from the original on 24 January 2021. Retrieved 17 December 2020.
Further reading
[edit]- Haselden, G. G. (1971), Cryogenic fundamentals, Academic Press, New York, ISBN 0-12-330550-0.
Cryogenics
View on GrokipediaDefinitions and Scope
Core Definition
Cryogenics is the scientific study of the production of very low temperatures and the behavior of materials under such conditions, generally defined as temperatures below approximately -150 °C (123 K).[8] This field encompasses the methods for achieving and maintaining these extremes, often extending down to near absolute zero, where unique physical properties emerge due to reduced thermal energy.[8] The conventional threshold aligns with the liquefaction points of permanent gases, such as nitrogen, which boils at 77.34 K (-195.81 °C) at standard atmospheric pressure.[9] A key distinction exists between cryogenics and general refrigeration: while refrigeration involves cooling to moderate low temperatures (typically above -100 °C) for practical applications like food preservation, cryogenics specifically targets the ultra-low regime below 120 K (-153 °C), emphasizing phenomena close to absolute zero that require specialized techniques beyond standard vapor-compression cycles. This focus enables investigations into superconductivity, superfluidity, and other quantum-scale effects not observable at higher temperatures.[8] In cryogenic research, the Kelvin (K) scale is the standard unit, as it is an absolute temperature scale beginning at 0 K, the theoretical point of zero molecular motion.[10] For reference, cryogenic ranges convert as follows: -150 °C equals 123.15 K, and -273.15 °C (absolute zero) is 0 K; equivalently, -238 °F corresponds to 123 K, and -459.67 °F to 0 K.[8] The term "cryogenics," derived from Greek roots meaning "cold-producing," was adopted in the late 19th and early 20th centuries to describe this domain of low-temperature physics, with its first documented use in 1894 by Heike Kamerlingh Onnes in the context of laboratory work at temperatures below -150 °C.[11]Related Fields
Cryobiology is a specialized field within the biological sciences that examines the effects of low temperatures on living organisms, tissues, and cells, with a primary focus on preserving biological materials through freezing techniques such as cryopreservation.[12] Unlike general cryogenics, which deals with the production, maintenance, and physical effects of extremely low temperatures (typically below -150°C) across materials and systems, cryobiology emphasizes the preservation of life processes and the mitigation of damage from ice formation or cellular stress during cooling.[13] This distinction highlights cryobiology's biological orientation, often applying cryogenic methods to applications like organ banking or fertility preservation, while cryogenics remains rooted in physics and engineering principles. Cryosurgery represents a medical application of cryogenic cooling, where extreme cold—generated by substances like liquid nitrogen or argon gas—is used to selectively destroy abnormal or cancerous tissues through controlled freezing.[14] It differs from core cryogenics by prioritizing therapeutic outcomes in clinical settings, such as tumor ablation, over the fundamental production or study of low temperatures themselves.[15] The procedure relies on cryogenic tools but focuses on precise tissue damage via freeze-thaw cycles, making it a procedural discipline rather than a broad scientific one.[16] Cryoelectronics explores the behavior and performance of electronic devices and circuits at cryogenic temperatures, particularly leveraging phenomena like superconductivity to enhance efficiency and reduce power losses in applications such as sensors, amplifiers, and computing systems. This field intersects with cryogenics through the need for low-temperature environments (often near absolute zero) to enable superconducting states in materials, but it is distinct in its emphasis on electronic functionality and integration, such as in Josephson junctions or SQUIDs for precise measurements.[17] Cryoelectronics thus builds on cryogenic infrastructure while advancing device-specific innovations in aerospace, quantum computing, and metrology.[18] Cryonics involves the post-mortem preservation of human bodies or brains at cryogenic temperatures, with the speculative goal of future revival through advanced nanotechnology or medical technology.[19] It is considered outside mainstream science due to the lack of evidence for successful reanimation and its reliance on unproven assumptions about reversing death and decay.[20] While drawing on cryogenic preservation techniques similar to those in cryobiology, cryonics extends into pseudoscientific territory by focusing on indefinite suspension for potential resurrection, without established scientific validation.[21] Cryoconservation refers to the long-term storage of animal and plant genetic resources—such as semen, embryos, oocytes, and tissues—through cryopreservation at ultra-low temperatures, primarily to support breeding programs and biodiversity conservation in agriculture.[22] Rooted in biological freezing methods, it links cryogenics to agricultural and ecological goals by safeguarding genetic diversity against extinction, but it is distinct in its focus on viable reproduction rather than general low-temperature physics.[23] This approach has become essential for global food security, enabling the regeneration of livestock and crop varieties from frozen repositories.[12]History and Etymology
Etymology
The term cryogenics derives from the Greek roots κρύος (kryos), meaning "icy cold" or "frost," and γενής (genēs), meaning "producing" or "generating," literally denoting the production of cold.[24] This nomenclature reflects the field's focus on generating and maintaining extremely low temperatures, typically below -150°C (123 K). The adjective "cryogenic" first appeared in scientific literature in 1894, coined by Dutch physicist Heike Kamerlingh Onnes in his paper "On the Cryogenic Laboratory at Leiden and on the Production of Very Low Temperatures," amid early experiments in gas liquefaction.[8] Preceding this, the related term cryogen emerged in 1875, introduced by British chemist and physicist Frederick Guthrie to describe substances capable of producing intense cold, such as liquefied gases used as refrigerants.[25] In the late 19th century, as liquefaction techniques advanced—exemplified by the first liquid oxygen production in 1877—terminology shifted from cryogen toward the more encompassing cryogenics, which by the early 20th century standardized to denote the broader science of low-temperature phenomena and technologies.[11] This etymology distinguishes cryogenics from refrigeration, the latter stemming from the Latin refrigerare ("to cool again" or "to make cool"), a term historically applied to moderate cooling processes like food preservation above cryogenic thresholds.[26] While both involve temperature reduction, cryogenics emphasizes the generation of ultralow temperatures enabling unique physical states, such as superconductivity.Historical Milestones
The development of cryogenics began in the late 19th century with pioneering efforts to liquefy so-called permanent gases, which had long resisted condensation under ordinary conditions. In 1877, French physicist Louis-Paul Cailletet and Swiss physicist Raoul Pictet independently achieved the first liquefaction of oxygen through rapid expansion and compression techniques, producing fleeting droplets of the liquid at temperatures around 90 K.[27] These experiments marked a breakthrough in low-temperature physics. Building on these advances, Scottish chemist and physicist James Dewar invented the vacuum flask, known as the Dewar flask, in 1892 to store cryogenic liquids without significant heat transfer.[28] This double-walled vessel, evacuated between silvered walls, enabled the safe handling and prolonged retention of liquefied gases like air and hydrogen, revolutionizing cryogenic experimentation.[29] In 1898, Dewar succeeded in liquefying hydrogen at 20.4 K using a continuous flow method with his flask, providing a crucial intermediate step toward even lower temperatures.[30] The early 20th century saw further milestones in achieving even lower temperatures. In 1908, Dutch physicist Heike Kamerlingh Onnes at Leiden University succeeded in liquefying helium for the first time, reaching a boiling point of 4.2 K under atmospheric pressure using a complex cascade refrigeration system.[31] This accomplishment, which required purifying helium from natural gas sources and employing liquid hydrogen as an intermediate coolant, opened access to temperatures just above absolute zero.[32] Three years later, in 1911, Onnes discovered superconductivity while studying the electrical resistance of mercury cooled in liquid helium; at 4.2 K, the resistance dropped abruptly to zero, revealing a new quantum state of matter.[33] Onnes's work on superconductivity earned him the 1913 Nobel Prize in Physics. Industrial applications emerged in the 1910s and 1920s with the Claude process, developed by French engineer Georges Claude, which enabled efficient large-scale separation of air into oxygen, nitrogen, and rare gases through regenerative cooling and expansion work.[34] This method, commercialized by Air Liquide, scaled cryogenic production for welding and medical uses, producing tons of liquid oxygen daily by the 1920s.[35] Following World War II, cryogenic technologies expanded significantly in rocketry, with liquid oxygen and hydrogen adopted as propellants in programs like the U.S. Saturn V rocket, necessitating advanced storage and handling systems for space exploration.[5] In the mid-20th century, key figures like Soviet physicist Pyotr Kapitza advanced the field through studies of liquid helium. Kapitza's 1937 discovery of superfluidity in helium-II below 2.17 K—where the liquid exhibits zero viscosity and flows without friction—earned him the 1978 Nobel Prize in Physics for low-temperature innovations.[36] Concurrently, the 1960s brought dilution refrigerators, first realized experimentally in 1964 by leveraging the phase separation and mixing of helium-3 and helium-4 isotopes to achieve millikelvin temperatures (down to about 0.01 K) continuously.[37] These devices, proposed by Heinz London in the 1950s, extended cryogenic capabilities for precise low-temperature research.[38] Entering the 21st century, cryogenics has integrated with quantum technologies, particularly in the 2020s with scalable dilution refrigerator systems supporting superconducting qubit arrays for quantum computing.[39] These ultra-low-temperature platforms, operating below 20 mK, mitigate thermal noise in multi-qubit processors, as demonstrated in recent prototypes exceeding 100 qubits with improved coherence times.[40] Such developments build on Onnes's foundational superconductivity discoveries, enabling fault-tolerant quantum systems.[41]Fundamental Principles
Thermodynamic Basics
Cryogenics relies on fundamental thermodynamic principles to achieve and maintain temperatures below 120 K, primarily through processes that exploit gas behavior under expansion and the limits imposed by entropy at low temperatures. These principles govern heat transfer, phase changes, and energy exchanges in cryogenic systems, enabling efficient cooling without violating the laws of thermodynamics. The Joule-Thomson effect is a key mechanism for cryogenic cooling, involving the isenthalpic throttling of real gases through a porous plug or valve, where the gas temperature decreases upon expansion due to intermolecular forces.[42] This cooling occurs when the process operates below the gas's inversion temperature, above which heating may result instead. For nitrogen, a common cryogenic fluid, the inversion temperature is approximately 621 K.[43] The magnitude of this temperature change is quantified by the Joule-Thomson coefficient, defined as where indicates cooling for gases like nitrogen below the inversion temperature. Adiabatic expansion and compression cycles form the basis of many cryogenic refrigeration systems, such as the Brayton cycle, where a gas is compressed adiabatically to raise its pressure and temperature, cooled at constant pressure, and then expanded adiabatically to produce cooling work. In the expansion step, the gas performs work without heat exchange, lowering its temperature significantly; this is more efficient than isenthalpic expansion for liquefaction processes. Compression increases the gas's internal energy, preparing it for heat rejection to a warmer reservoir, thereby enabling continuous cooling in closed-loop systems.[44] The third law of thermodynamics imposes fundamental limits on cryogenic processes, stating that the entropy of a perfect crystal approaches a minimum value (often zero) as temperature nears absolute zero, making it impossible to reach 0 K in finite steps. As temperatures decrease, the heat capacity of materials approaches zero, reducing the energy required to lower the temperature further but also complicating heat removal since entropy changes () become vanishingly small.[45] This law underscores the asymptotic approach to absolute zero in cryogenic cooling, where each successive temperature reduction demands exponentially more effort. Phase transitions in cryogenic substances, particularly boiling and critical points, are critical for liquefaction and storage. For example, nitrogen boils at 77 K at atmospheric pressure, transitioning from gas to liquid and absorbing latent heat.[46] The critical point, beyond which distinct liquid and gas phases do not exist, occurs for nitrogen at 126.2 K and 3.39 MPa, influencing the design of high-pressure cryogenic systems. Similar transitions apply to helium (boiling at 4.2 K at 1 atm, critical at 5.2 K and 0.227 MPa) and oxygen (boiling at 90 K at 1 atm, critical at 154.6 K and 5.04 MPa), dictating operational pressures and temperatures in cryogenic applications.[46]Low-Temperature Phenomena
At cryogenic temperatures, quantum mechanical effects dominate the behavior of matter, leading to emergent phenomena that defy classical physics. These include macroscopic quantum states where particles collectively exhibit wave-like properties, resulting in zero resistance to flow or expulsion of magnetic fields. Such behaviors are observable only when thermal energy is minimized, allowing quantum coherence to prevail over disorder.[47] Superconductivity manifests as zero electrical resistance in certain materials below a critical temperature , enabling persistent currents without energy loss. This phenomenon was first observed in mercury by Heike Kamerlingh Onnes in 1911 at 4.2 K, but its quantum nature was later elucidated. A hallmark is the Meissner effect, where superconductors expel magnetic fields from their interior, creating perfect diamagnetism; this was discovered in 1933 by Walther Meissner and Robert Ochsenfeld using lead and tin samples cooled below their .[47][48] The microscopic explanation for conventional superconductivity is provided by Bardeen-Cooper-Schrieffer (BCS) theory, which posits that electrons form Cooper pairs mediated by lattice vibrations (phonons), allowing them to condense into a single quantum state. The critical temperature is approximated by the formula where is the characteristic phonon energy, is the density of states at the Fermi level, and is the pairing interaction strength; this relation highlights the exponential sensitivity to the pairing mechanism. Developed in 1957, BCS theory successfully predicts properties like the energy gap and isotope effect, establishing the pairing as an attractive interaction overcoming Coulomb repulsion at low energies.[48] Superfluidity, another quantum phenomenon, occurs in liquid helium-4 below the lambda point of 2.17 K, where it transitions to a state of zero viscosity, allowing frictionless flow through narrow channels and even climbing container walls against gravity via the "fountain effect." This was independently discovered in 1937–1938 by Pyotr Kapitsa in Moscow and by John F. Allen and Donald Misener in Cambridge, revealing helium II's ability to support persistent flow rates exceeding 10 cm/s without dissipation. The lambda point marks a second-order phase transition driven by Bose statistics, with superfluidity arising from a macroscopic occupation of the ground state.[49] Bose-Einstein condensation (BEC) represents the ultimate quantum degeneracy, where a dilute gas of bosons cools to microkelvin temperatures and collapses into a single coherent wavefunction, behaving as a single giant atom. First realized experimentally in 1995 by Eric Cornell and Carl Wieman using laser and evaporative cooling on rubidium-87 atoms at approximately 170 nK, this achievement confirmed predictions from 1924–1925 by Satyendra Nath Bose and Albert Einstein, enabling studies of superfluidity and vortex dynamics in ultracold regimes. The condensate forms when the de Broglie wavelength exceeds the interparticle spacing, typically requiring densities around atoms/cm³.[50][51] To sustain these phenomena, cryogenic insulation minimizes heat ingress, primarily through vacuum insulation, which suppresses gaseous conduction and convection, and multilayer insulation (MLI), consisting of 10–100 alternating layers of reflective foil (e.g., aluminized Mylar) and spacers in a high vacuum (below torr). MLI reduces radiative heat transfer by factors of 100–1000 compared to single-layer systems, with effective emissivities on the order of 0.001 or lower;[52] NASA applications demonstrate heat flux reductions to below 1 W/m² at 77 K boundaries. These methods exploit the Stefan-Boltzmann law's dependence, making them essential for maintaining temperatures near absolute zero.Cryogenic Substances
Cryogenic Fluids
Cryogenic fluids are liquefied gases maintained at temperatures below -150°C (123 K), exhibiting unique physical properties that make them essential for cooling, preservation, and industrial processes. These fluids, including liquid nitrogen, liquid helium, liquid oxygen, and liquid hydrogen, are valued for their low boiling points, high densities in liquid form compared to gases, and varying thermal conductivities that enable efficient heat transfer at cryogenic conditions. Their inertness, reactivity, or energy content determines specific applications, such as general cooling or specialized ultra-low temperature environments.[53] Liquid nitrogen (LN₂) boils at 77 K under atmospheric pressure and has a density of approximately 806 kg/m³ at that temperature, making it an inert, cost-effective coolant widely used in laboratories and food preservation due to its non-reactive nature and abundance. Its thermal conductivity in the liquid state is about 0.14 W/m·K, facilitating moderate heat dissipation. Liquid helium (LHe), with a boiling point of 4.2 K and density of 125 kg/m³, is crucial for achieving ultra-low temperatures, such as in superconductivity experiments; notably, below the lambda point (2.17 K), superfluid helium II exhibits extraordinarily high thermal conductivity, approaching infinite values in certain conditions, which enhances its utility in precision cooling. Liquid oxygen (LOX) boils at 90 K with a density of 1,141 kg/m³ and thermal conductivity around 0.15 W/m·K, serving as a powerful oxidizer in various chemical processes. Liquid hydrogen (LH₂), boiling at 20 K and with a low density of 71 kg/m³, acts as a clean fuel source, its thermal conductivity of about 0.12 W/m·K supporting efficient energy transfer in cryogenic systems.[53][54][53] The physical properties of these fluids, such as their boiling points and densities, are critical for system design, as they influence phase transitions and storage requirements; for instance, helium's low density necessitates larger volumes for equivalent mass compared to denser fluids like LOX. Thermal conductivity variations, particularly helium's enhancement in superfluid states, allow for superior cooling in quantum technologies without mechanical pumps. These properties are derived from equation-of-state models validated against experimental data, ensuring accurate predictions for engineering applications.[53][54]| Fluid | Boiling Point (K) | Density (kg/m³ at BP) | Thermal Conductivity (W/m·K, liquid at BP) | Key Characteristics |
|---|---|---|---|---|
| Liquid Nitrogen (LN₂) | 77 | 806 | 0.14 | Inert, inexpensive, general cooling |
| Liquid Helium (LHe) | 4.2 | 125 | ~0.025 (He I); very high in He II | Ultra-low temp, superfluidity |
| Liquid Oxygen (LOX) | 90 | 1,141 | 0.15 | Oxidizer, reactive |
| Liquid Hydrogen (LH₂) | 20 | 71 | 0.12 | Fuel, low density |
Cryogenic Materials
Cryogenic materials encompass a range of solids and composites engineered to withstand extreme low temperatures, typically below 120 K, while maintaining desirable mechanical, thermal, and electrical properties for applications in storage, transportation, and scientific instrumentation. These materials must resist thermal stresses, preserve structural integrity, and often exhibit enhanced performance, such as increased strength or superconductivity, at cryogenic conditions. Selection criteria prioritize low thermal expansion to minimize dimensional changes, high thermal conductivity for heat transfer in certain components, and resistance to brittleness, ensuring reliability in environments like liquid helium (4.2 K) or liquid nitrogen (77 K) systems. Among metals suitable for cryogenic use, austenitic stainless steels, such as grades 304 and 316, are favored for their low coefficient of thermal expansion, which reduces contraction-induced stresses during cooling; for instance, the linear thermal expansion of 304 stainless steel is approximately 8 × 10^{-6} K^{-1} between 4 K and 300 K.[59] These steels retain ductility and toughness at low temperatures due to their face-centered cubic structure, avoiding the embrittlement seen in other alloys. Aluminum alloys, like 6061-T6, are selected for their high thermal conductivity, which increases dramatically at cryogenic temperatures—reaching approximately 200 W/m·K near 20 K—making them ideal for heat exchangers and structural components requiring efficient thermal management.[60] Superconducting materials represent a critical class of cryogenic solids, exhibiting zero electrical resistance and perfect diamagnetism below their critical temperature (T_c). Type I superconductors, such as lead, display a sharp transition and complete Meissner effect but are limited to low magnetic fields; lead, for example, has a T_c of 7.2 K and was among the earliest discovered elemental superconductors. In contrast, Type II superconductors allow partial magnetic flux penetration via vortices, enabling higher field applications; niobium-titanium (NbTi) alloy, with a T_c of approximately 9.5 K, is widely used in superconducting magnets for MRI and particle accelerators due to its ability to generate fields up to 9.5 T at 4.2 K when carrying current densities exceeding 3000 A/mm².[61][62] Polymers and composites serve primarily as thermal insulators in cryogenic systems, where minimizing heat leak is essential. Aerogels, particularly silica-based variants reinforced with fibers, offer exceptionally low thermal conductivity (k-factor) values, such as 0.013 W/m·K at ambient conditions, which decrease further at cryogenic temperatures to around 0.010 W/m·K, outperforming traditional insulations like polyurethane foam by up to 50% in reducing boil-off rates in liquefied gas storage. These lightweight materials (density ~0.15 g/cm³) provide mechanical flexibility and hydrophobic properties, making them suitable for pipe insulation and tank linings.[63] A key challenge in cryogenic materials is embrittlement, where certain alloys undergo a ductile-to-brittle transition at low temperatures, leading to sudden fracture under stress. For ferritic steels, this transition occurs below approximately 100 K, as reduced atomic mobility hinders dislocation movement, causing cleavage fracture instead of plastic deformation; impact toughness can drop from over 200 J at room temperature to below 20 J at 77 K. Austenitic stainless steels mitigate this issue, but careful alloy selection and welding techniques are required to prevent microcracking in composite structures. Recent developments have focused on high-temperature superconductors (high-T_c), expanding cryogenic applications beyond liquid helium. The discovery of yttrium barium copper oxide (YBCO), a cuprate ceramic with a T_c of 93 K, in 1987 enabled superconductivity above the boiling point of liquid nitrogen (77 K), revolutionizing magnet technology and permitting more accessible cooling methods. This breakthrough, achieved through solid-state synthesis and characterized via resistivity and magnetic susceptibility measurements, has led to practical wires and tapes for high-field applications, though challenges like weak intergrain coupling persist.[64]| Superconductor Type | Example | Critical Temperature (T_c) | Key Application |
|---|---|---|---|
| Type I | Lead | 7.2 K | Fundamental research |
| Type II | NbTi | 9.5 K | Superconducting magnets |
| High-T_c | YBCO | 93 K | High-field devices with LN2 cooling |