Superconductivity and Liquid Helium II Phenomena

Total Page:16

File Type:pdf, Size:1020Kb

Superconductivity and Liquid Helium II Phenomena 604 NATURE NOVEMBER 21, 1942, VOL. 150 Superconductivity and Liquid Helium II phenomena . Indeed the shape of these curves is similar; they both start with a finite slope at the WHEN discussing our observations on the transfer temperature at which the first anomalous behaviour of liquid helium II along solid surfaces above the is evident, and they both become temperature in­ liquid level', we pointed out that this mechanism of dependent near absolute zero. surface flow might also be responsible for the 'trans­ (6) When developing the thermodynamics of a port phenomena' in the bulk liquid (high heat con­ superconductor with the current density rather than duction, low viscosity and the fountain effect)•. the magnetic field as the variable of state, one arrives Subsequent experiments by ourselves 3, Allen and at a formalism which also fits well the observations Rookie' and by Kapitza• strongly support this in liquid helimn II. While the rigorous derivation assumption. It appears that the transfer film of this cannot be given here, it appears that R• observed above the liquid level also extends below it, assumes the same significance in determining the covering all solid surfaces in contact with liquid free energy of liquid helium II as the square of the helium II, and it is evidently in this film that the threshold field has for superconductors•. anomalous transport phenomena take place. (7) One would expect that in such a model the It has been suggested by F. London6 that the specific heat of the system of superconductive elec­ )..phenomenon in helimn may be caused by the trons as well as that of the 'unexcited' helimn atoms existence of helium atoms of very low (or zero) would be zero. This seems actually to be the case. thermal energy, and the mechano-caloric effect The facts that a super-current in a temperature found by us• strengthens this view. This effect shows gradient produces no Thomson heat8 and that no that by flow along a solid surface, such thermally heat transport exists in a helium film in a direction 'unexcited' atoms can be separated to a certain ex­ opposite to that of the fiow 1 strongly suggest that tent from the bulk liquid. no heat is transferred to the particles while they In elaborating our hypothesis we have now come remain in the anomalous state. We ascribe the ob­ across a striking analogy between the phenomenology served high specific heat of superconductive metals of liquid helium II and superconductivity, which and liquid helimn II to the energy taken up in lifting seems to go much farther than a superficial similarity. particles from the lowest state into thermal equili­ While we have a good deal of information on the brimn with the rest of the substance. superconductive state, our knowledge concerning The question naturally arises what physical liquid helium II is very limited. A certain amount of significance has to be given to this striking analogy. generalization has thus been necessary in the formula­ It seems to us that the fundamental phenomenon is tion of our thesis, which therefore must be considered the passing at finite temperatures of a number of as of an approximate nature only. The main points particles into the lowest quantum state, where no of the analogy are as follows : energy exchange can take place between them and (I) As it is impossible to establish a difference of the remainder of the substance. This new form of electrical potential at the ends of a superconductor, aggregation of matter evidently follows quite general so it is impossible to establish a temperature difference ru1es, so that the fact that the particles are electrons along the transfer film of helium II. in one case and atoms in the other is only of secondary (2) In both cases the frictionless transport of importance. The phenomenon of frictionless trans­ particles (electrons or atoms) breaks down as soon port confined, as it is in both cases, to the geometrical as a certain value of flow is exceeded. This limiting surface, might be explained by the fact that, as the value is given by the current threshold in super­ particles are free from interaction with the bulk of conductors, J, and by the rate of transfer, R, in the substance, they can only be accelerated by ex­ helimn1• ternal forces. The range to which these external (3) In both cases this limiting value of flow is forces can p enetrate the substance limits the layer solely dependent on temperature and is independent in which the transport takes place. Thus, in a super­ of the length of the path the particles have to travel. conductor, electrons can only be moved within the It is directly proportional to the width of the con­ depth of penetration of an external magnetic field•, necting surface (this holds rigidly for plane surfaces, while the flow in a helium film is limited by the whereas for curved surfaces the limiting rate of flow extent of the van der Waals' forces of the container. will be reduced in both cases). It appears from these considerations that the (4) In liquid helium as well as in superconductors, theoretical interpretations of the superconductive the frictionless transport seems to be confined to the state and of the ).-phenomenon in liquid helium II geometrical surface of the substance. Kapitza6 has should be similar in their fundamental aspect, and demonstrated that an anomalously high heat con­ it is with regard to such a generalized theoretical duction does not take place in the bulk of helimn II ; treatment that we hope the analogy pointed out in that is, there is no frictionless transport of atoms this note will be of value. unless this can take place along a solid - liquid J. G. DAUNT. boundary surface. An analogy t o this exists in a Clarendon Laboratory, K. MENDELSSOHN. superconductor, since it seems theoretically im­ Oxford. possible to remove an electric charge from inside a Nov. 5. completely closed superconducting shell except by 1 Daunt and Mendelssohn, Proc. Roy. Soc., A, 170, 423 (1939). the process of normal conduction. 1 See, for example, Darrow, Rev. Mod. Phya.J.. 12, 257 (1940), and (5) It appears that in both cases the maximum Jones, "Reports on Progress In Physics", o, 280 (1940). cw·rent density of flow on the surface (J, R) indicates 1 Daunt and NATURE, 143, 719 (1939). the number of particles which can at each tempera­ • Allen and Iteekle, NATURE, 144, 475 (1939). ture be transported frictionlessly (provided one 'Kapitza, J. Phya. U.S.S.R., <I, 181 (1941). assumes the particles to have velocities independent 1 London, F ., Phvs. Rev., 54, 947 (19:!8). of temperature ). The threshold curve and the curve ' Gorter and Casimir, 1, 30f> (1934). giving the temperature dependency of R will there­ • Daunt and 'Mendelssohn, NATURB, 141, 116 (1938). fore play an identical part in the treatment of both • London, H ., Proc. Roy. Soc., A, 152, 650 (1935). © 1942 Nature Publishing Group.
Recommended publications
  • Liquid Helium Variable Temperature Research Dewars
    CRYO Variable Temperature Liquid Helium Research Dewars CRYO Variable Temperature Liquid Helium Research Dewars Cryo Industries Variable Temperature Liquid Helium Research Dewars (CN Series) provide soluitions for an extensive variety of low temperature optical and non-optical requirements. There are numerous designs available, including Sample in Flowing Vapor, Sample in Vacuum and Sample in Exchange Gas. Our most popular models features Sample in Flowing Vapor (dynamic exchange gas), where the sample is cooled by insertion into flowing helium gas exiting from the vaporizer (also known as the diffuser or heat exchanger). The samples are top loading and can be quickly changed while operating. The temperature of the sample can be varied from typically less than 1.4 K to room temperature. Liquid helium flows from the reservoir through the adjustable flow valve down to the vaporizer located at the bottom of the sample tube. Applying heat, vaporizes the liquid and raises the gas temperature. This gas enters the sample zone to cool the sample to your selected temperature. Pumping on the sample zone will provide temperatures below 2 K with either sample in vapor or immersed in liquid. No inefficient liquid helium reservoir pumping is required. The system uses enthalpy (heat capacity) of the helium vapor which results in very high power handling, fast temperature change, ultra stable temperatures, ease of use an much more - Super Variable Temperature. Optical ‘cold’ windows are normally epoxy sealed, strain relief mounted into indium sealed mounts or direct indium mounted. Window seals are reliable and fully guaranteed. For experiments where flowing vapor may be undesirable (such as mossbauer or infrared detectors), static exchange gas cooling and sample in vacuum inserts are available.
    [Show full text]
  • Liquid Helium
    Safetygram 22 Liquid helium Liquid helium is inert, colorless, odorless, noncorrosive, extremely cold, and nonflammable. Helium will not react with other elements or compounds under ordinary conditions. Since helium is noncorrosive, special materials of construction are not required. However, materials must be suitable for use at the extremely low temperatures of liquid helium. Vessels and piping must be selected and designed to withstand the pressure and temperatures involved and comply with applicable codes for transport and use. Manufacture Most of commercial helium is recovered from natural gas through a cryogenic separation process. Normally, helium is present in less than 1% by volume in natural gas. Helium is recovered, refined, and liquefied. Liquid helium is typically shipped from production sources to storage and transfill facilities. Tankers, ranging in size from 5,000 to 11,000 gallons, contain an annular space insulated with vacuum, nitrogen shielding, and multilayer insulation. This de- sign reduces heat leak and vaporization of liquid helium during transportation. Uses The extremely low temperature of liquid helium is utilized to maintain the superconducting properties of magnets in applications such as MRI, NMR spectroscopy, and particle physics research. The main application for gas- eous helium is for inert shielding gas in metal arc and laser welding. Helium provides a protective atmosphere in the production of reactive metals, such as titanium and zirconium. Gaseous helium is used as a coolant during the draw- ing of optical fibers, as a carrier gas for chromatography, and as a leak detection gas in a variety of industries. Being both lighter than air and nonflammable, helium is used to inflate balloons and airships.
    [Show full text]
  • Helium, Refrigerated Liquid
    Helium, Refrigerated Liquid Safety Data Sheet P-4600 This SDS conforms to U.S. Code of Federal Regulations 29 CFR 1910.1200, Hazard Communication. Issue date: 01/01/1979 Revision date: 01/31/2021 Supersedes: 09/08/2020 Version: 2.0 SECTION: 1. Product and company identification 1.1. Product identifier Product form : Substance Trade name : Liquid Helium CAS-No. : 7440-59-7 Formula : He Other means of identification : Helium, Refrigerated Liquid; Helium-4; Refrigerant Gas R-704 1.2. Relevant identified uses of the substance or mixture and uses advised against Use of the substance/mixture : Industrial use; Use as directed. Diving Gas (Underwater Breathing) 1.3. Details of the supplier of the safety data sheet Linde Inc. 10 Riverview Drive Danbury, CT 06810-6268 - USA 1.4. Emergency telephone number Emergency number : Onsite Emergency: 1-800-645-4633 CHEMTREC, 24hr/day 7days/week — Within USA: 1-800-424-9300, Outside USA: 001-703-527-3887 (collect calls accepted, Contract 17729) SECTION 2: Hazard identification 2.1. Classification of the substance or mixture GHS US classification Simple asphyxiant SIAS Press. Gas (Ref. Liq.) H281 2.2. Label elements GHS US labeling Hazard pictograms (GHS US) : GHS04 Signal word (GHS US) : Warning Hazard statements (GHS US) : H281 - CONTAINS REFRIGERATED GAS; MAY CAUSE CRYOGENIC BURNS OR INJURY OSHA-H01 - MAY DISPLACE OXYGEN AND CAUSE RAPID SUFFOCATION. Precautionary statements (GHS US) : P202 - Do not handle until all safety precautions have been read and understood. P271+P403 - Use and store only outdoors or in a well-ventilated place. P282 - Wear cold insulating gloves/face shield/eye protection.
    [Show full text]
  • Visualization of Two-Fluid Flows of Superfluid Helium-4 SPECIAL FEATURE
    Visualization of two-fluid flows of superfluid helium-4 SPECIAL FEATURE Wei Guoa,b, Marco La Mantiac, Daniel P. Lathropd, and Steven W. Van Scivera,b,1 aMechanical Engineering Department, Florida State University, Tallahassee, FL 32303; bNational High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310; cDepartment of Low Temperature Physics, Faculty of Mathematics and Physics, Charles University, 180 00 Prague, Czech Republic; and dDepartments of Physics and Geology, Institute for Research in Electronics and Applied Physics, and Institute for Physics Science and Technology, University of Maryland, College Park, MD 20742 Edited by Katepalli R. Sreenivasan, New York University, New York, NY, and approved December 13, 2013 (received for review July 17, 2013) Cryogenic flow visualization techniques have been proved in not kept pace, in part due to the extremely low temperature and recent years to be a very powerful experimental method to study low density of the fluid. A number of early efforts were devoted superfluid turbulence. Micron-sized solid particles and metastable to producing macroscopic particles for qualitative investigations helium molecules are specifically being used to investigate in (10–12) and the challenge of producing neutrally buoyant par- detail the dynamics of quantum flows. These studies belong to ticles that faithfully follow the complex flow fields has been the a well-established, interdisciplinary line of inquiry that focuses on main impediment to quantitative advancement. In addition, sev- the deeper understanding of turbulence, one of the open problem eral attempts have been made to visualize fluid dynamics in su- of modern physics, relevant to many research fields, ranging from perfluid helium with microscopic tracers, which include neutron fluid mechanics to cosmology.
    [Show full text]
  • The Noble Gases
    The Noble Gases The Noble Gases (inert gases, Group 0, Group 18 or the helium group) are notoriously unreactive elements (‘noble’ means unreactive in chemistry) and in their elemental state they exist as monoatomic gases – gases whose ‘molecules’ are single atoms of the element, since the atoms are reluctant to react with anything, including one-another. This inertness is due to the fact that they have stable outer electron shells, with stable octets of electrons (full s and p subshells) except helium, which has a stable full inner shell. The electronic configurations are: Helium (He): 1s2 Neon (Ne): 1s2 2s2 2p6 Argon (Ar): [Ne] 3s2 3p6 Krypton (Kr): [Ar] 3d10 4s2 4p6 Xenon (Xe): [Kr] 4d10 5s2 5p6 Radon (Rn): [Xe] 5d10 6s2 6p6 Nevertheless, this group does have some interesting chemistry and also exhibit interesting physical properties. Reactivity increases down the group. Often helium is included as the first member of the group. Helium (He) Helium is chemically a highly unreactive element. It only forms transient species when electric discharges are passed through a mixture of helium gas and another gaseous element. for example, passing an electric discharge through a mixture of helium and hydrogen forms the transient molecule HHe, which has a very short half-life. HHeF is metastable. Neon (Ne) Neon is chemically the most unreactive element. It forms no true compounds, and no neutral molecules. Ionic molecules are known, e.g. (NeAr)+, (NeH)+, (HeNe)+ and Ne+. Argon (Ar) The unstable argon fluorohydride, HArF, is known. Ar also forms clathrates (see krypton) with water and highly unstable ArH+ and ArF are known.
    [Show full text]
  • The Noble Gases
    INTERCHAPTER K The Noble Gases When an electric discharge is passed through a noble gas, light is emitted as electronically excited noble-gas atoms decay to lower energy levels. The tubes contain helium, neon, argon, krypton, and xenon. University Science Books, ©2011. All rights reserved. www.uscibooks.com Title General Chemistry - 4th ed Author McQuarrie/Gallogy Artist George Kelvin Figure # fig. K2 (965) Date 09/02/09 Check if revision Approved K. THE NOBLE GASES K1 2 0 Nitrogen and He Air P Mg(ClO ) NaOH 4 4 2 noble gases 4.002602 1s2 O removal H O removal CO removal 10 0 2 2 2 Ne Figure K.1 A schematic illustration of the removal of O2(g), H2O(g), and CO2(g) from air. First the oxygen is removed by allowing the air to pass over phosphorus, P (s) + 5 O (g) → P O (s). 20.1797 4 2 4 10 2s22p6 The residual air is passed through anhydrous magnesium perchlorate to remove the water vapor, Mg(ClO ) (s) + 6 H O(g) → Mg(ClO ) ∙6 H O(s), and then through sodium hydroxide to remove 18 0 4 2 2 4 2 2 the carbon dioxide, NaOH(s) + CO2(g) → NaHCO3(s). The gas that remains is primarily nitrogen Ar with about 1% noble gases. 39.948 3s23p6 36 0 The Group 18 elements—helium, K-1. The Noble Gases Were Kr neon, argon, krypton, xenon, and Not Discovered until 1893 83.798 radon—are called the noble gases 2 6 4s 4p and are noteworthy for their rela- In 1893, the English physicist Lord Rayleigh noticed 54 0 tive lack of chemical reactivity.
    [Show full text]
  • How to Fill with Liquid Helium
    How to Fill with Liquid Helium These instructions are an introduction (or a reminder) of how to transfer liquid helium from a dewar to an instrument such as a magnet or a cryostat. In many cases you will want to pre-cool with liquid nitrogen, which is much more efficient that helium for cooling from room temperature to 80 K. Specific details about the instrument are available in the appropriate instruction manuals. 1. Make sure to always wear safety glasses and gloves whenever transferring liquid helium or liquid nitrogen. Also make sure that anyone you are working with or who is in the area is wearing safety glasses and is aware of what you are doing. 2. On the dewar, open the top valve and close the pressure relief valve. 3. Slowly put the transfer tube into the dewar. Make sure the pressure gauge is firmly seated and slide the tube all the way to the bottom. 4. On the instrument, open the helium fill port and the helium exhaust port. 5. If the cryostat is warm (does not have any helium in it), you can put the transfer tube into the helium fill port at once. If you are refilling an instrument, do not put the transfer line in until liquid is coming out (otherwise you will blow out what liquid is in the instrument with high pressure gas from the dewer). Liquid is coming from the tube when you see a thick white plume of gas. 6. To force liquid through the transfer tube, you need to maintain a pressure of 3-5 psi on the dewar.
    [Show full text]
  • How Liquid Helium and Superconductivity Came to Us
    IEEE/CSC & ESAS EUROPEAN SUPERCONDUCTIVITY NEWS FORUM (ESNF), No. 16, April 2011 Heike Kamerlingh Onnes and the Road to Liquid Helium Dirk van Delft, Museum Boerhaave – Leiden University e-mail: [email protected] Abstract – I sketch here the scientific biography of Heike Kamerlingh Onnes, who in 1908 was the first to liquefy helium and in 1911 discovered superconductivity. A son of a factory owner, he grew familiar with industrial approaches, which he adopted and implemented in his scientific career. This, together with a great talent for physics, solid education in the modern sense (unifying experiment and theory) proved indispensable for his ultimate successes. Received April 11, 2011; accepted in final form April 19, 2011. Reference No. RN19, Category 11. Keywords – Heike Kamerligh Onnes, helium, liquefaction, scientific biography I. INTRODUCTION This paper is based on my talk about Heike Kamerlingh Onnes (HKO) and his cryogenic laboratory, which I gave in Leiden at the Symposium “Hundred Years of Superconductivity”, held on April 8th, 2011, the centennial anniversary of the discovery. Figure 1 is a painting of HKO from 1905, by his brother Menso, while Figure 2 shows his historically first helium liquefier, now on display in Museum Boerhaave of Leiden University. Fig. 1. Heike Kamerling Onnes (HKO), 1905 painting by his brother Menso. 1 IEEE/CSC & ESAS EUROPEAN SUPERCONDUCTIVITY NEWS FORUM (ESNF), No. 16, April 2011 Fig. 2. HKO’s historical helium liquefier (last stage), now in Museum Boerhaave, Leiden. I will address HKO’s formative years, his scientific mission, the buiding up of a cryogenic laboratory as a direct consequence of this mission, add some words about the famous Leiden school of instrument makers, the role of the Leiden physics laboratory as an international centre of low temperature research, to end with a conclusion.
    [Show full text]
  • An Equation of State for Helium
    KTS04-2 An Equation of State for Helium A Kerley Technical Services Research Report December 2004 P.O. Box 709 Appomattox, VA 24522-0709 Tel: (434) 352-8400 I Fax: (434) 352-4973 I E-mail: [email protected] KTS04-2 An Equation of State for Helium A Kerley Technical Services Research Report Gerald I. Kerley December 2004 ABSTRACT This report describes a new equation of state (EOS) for helium. The PAN- DA code was used to construct separate EOS tables for the solid and fluid phases. The solid and fluid EOS were then assembled into a multiphase EOS table using the PANDA phase transition option. Contributions from thermal electronic excitation and ionization were also included in the mod- el. The EOS gives very good agreement with all static and shock-wave da- ta, except at temperatures below 20K, where further work is needed. This EOS was developed primarily for use in models of the giant planets, the sun, and stars but should be useful in other applications as well. P.O. Box 709 Appomattox, VA 24522-0709 Tel: (434) 352-8400 I Fax: (434) 352-4973 I E-mail: [email protected] CONTENTS CONTENTS FIGURES.............................................................................................................................3 TABLES ..............................................................................................................................3 1. INTRODUCTION .......................................................................................................4 2. MODEL OVERVIEW..................................................................................................5
    [Show full text]
  • How to Transfer Liquid Helium Liquid Helium (Lhe) Is Needed to Operate Our Measurement Systems and the Magnets There Should Have
    How to transfer liquid Helium Liquid Helium (LHe) is needed to operate our measurement systems and the magnets there should have a certain minimum level of LHe. The transfer is a bit more complex comparing to the handling of liq. Nitrogen. This has a number of reasons: First of all, LHe evaporates very fast when exposed to air and vacuum isolated transfer systems are needed. Second, LHe is expensive and losses must be avoided. And finally, for LHe the safety requirements are quite restrictive: The contact with LHe and also with cold Helium gas immediately causes severe burns, comparable to a 3000 °C welding flame. In the following the process is described step by step. However, unexperienced persons must seek assistance from trained lab stuff. Without personal training it is forbidden to transfer Helium. 1. The equipment: Before starting a transfer, check that everything necessary is there: - Protective gloves and face protection - LHe level meter for the LHe vessel - Transfer syphon that matches the LHe vessel and the cryostat port. - A heat gun (max. 200 °C). 2. Next check the cryostat and the storage vessel: - The pressure gauge at the storage vessel must show less than 50mbar. - Check the LHe level in the vessel using the level meter. You may need 50-80%. - The cryostat status vessel be judged from the boil off rate seen at a “ball”. It must be resting in the low position. 3. Prepare cryostat and storage can: - Make sure that the valves at the recovery line are both open. - At the cryostat syphon entry, replace the plug with the recovery line.
    [Show full text]
  • HELIUM-3 for Researchers CIA CRYO Industries of America, Inc
    26 years of making cryogenics HELIUM-3 for Researchers www.cryoindustries.com CIA CRYO Industries of America, Inc. He-3 Cryostats - Sample in vacuum or top loading into vapor/liquid • Lowest base temperature due to advanced synthetic charcoal technology • Versatile 3-way charcoal sorb cooling system for lowest vibration and sub cooling • Flex circuits for quick & easy wire installation/removal and automatic thermal anchoring • Can be integrated into our high efficiency optical & non-optical cryostats, superconducting magnet systems, storage (transport) dewars or into your existing system. Helium-3 Introduction The basic principles of He3 inserts are indicated by the following three steps, 1,2,3. Warm the charcoal to release the adsorbed He3 gas which is then condensed by the 1 K POT. The 1liquid helium-3 collects in the He-3 pot, cooling the sample. Lowering the charcoal temperature to 4 K cryopumps the liquid He3 lowering its temperature . The isotope He3 is used instead of He4 because it does not exhibit film creep and a lower pressure can be 2reached (lower pressure means lower temperature). 3Collect the He3 gas back into the sorb and reuse - over and over and over again. He-3 gas He-3 gas in sorb back in sorb No gas left in charcoal sorb 1 K POT Condensing Pumped He-4 surfaces He-3 pot (empty) Liquid He-3 He-3 pot Sample mount (full) (empty) - 2 - Advanced Sorb Technology New charcoal technology provides for the higher pumping speeds - needed to cool the sample to less than 260 mK. 1200 Cooling Power Versus Temperature 1000 He-3 (SV std) W) μ 800 Screenshot taken during actual test of cryostat no.
    [Show full text]
  • Application of Quantum Mechanics to Liquid Helium
    CHAPTER I1 APPLICATION OF QUANTUM MECHANICS TO LIQUID HELIUM BY R. P. FEYNMAN CALIFORNIAINSTITUTE OF TECHNOLOGY,PASADENA, CALIFORNIA CONTENTS:1. Introduction, 17. - 2. Summary of the Theoretical Viewpoint, 18. - 3. Landau’s Interpretation of the Two Fluid Model, 20. - 4. The Reason for the Scarcity of Low Energy States, 26. - 6. Rotons, 31. - 0. Irrotational Superfluid Flow, 34. - 7. Rotation of the Superfluid, 36. - 8. Roperties of Vortex Lines, 40. - 9. Critical Velocity and Flow Resis- tance, 46. - 10. Turbulence, 48. - 11. Rotons as Ring Vortices, 61. 1. Introduction Liquid helium exhibits quantum mechanical properties on a large scale in a manner somewhat differently than do other substances. No other substance remains liquid to a temperature low enough to ex- hibit the effects. These effects have long been a puzzle. It is supposed that they can all be ultimately understood in terms of the properties of Schrddinger’s equation. We cannot expect a rigorous exposition of how these prgperties arise. That could only come from complete solutions of the Schr6dinger equation for the los8 atoms in a sample of liquid. For helium, as for any other substance today we must be satisfied with some approximate understanding of how, in principle, that equation could lead to solutions which indicate behavior similar to that observed. Since the discovery of liquid helium considerable progress has been made in understanding its behavior from first principles. Some of the properties are more easily understood than others. The most difficult of these concern the resistance to flow above critical velocity. If we permit some conjectures of Onsager l, however, perhaps a start has been made in understanding even these.
    [Show full text]