Cryogenic Processing: A Study of Materials at Low Temperatures
Cryogenic Processing: A Study of Materials at Low Temperatures
Cryogenic Processing: A Study of Materials at Low Temperatures
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Susheel Kalia
Received: 24 August 2009 / Accepted: 17 November 2009 / Published online: 26 November 2009
© Springer Science+Business Media, LLC 2009
1 Introduction
Cryogenic and refrigeration technology share a common history. The most obvious
difference between two is the temperature range. Cryogenics had its beginning in the
mid of 19th century when for the first time man learned to cool objects to a tempera-
ture lower than had ever existed naturally on the surface of earth. First practical vapor
compression refrigerator was invented by James Harrison in 1855. In 1872, Sir James
Dewar invented the vacuum flask. The air first liquefied in 1883 by Polish scientist
S. Kalia ()
Material Science Laboratory, Singhania University, Pacheri Bari, Dist. Jhunjhunu,
333 515 Rajasthan, India
e-mail: [email protected]
S. Kalia
e-mail: [email protected]
J Low Temp Phys (2010) 158: 934–945 935
named Olszewski. Ten years later Olszewski and a British scientist Sir James Dewar
liquefied hydrogen. In 1902, Georges Claude improved the efficiency of air liquefac-
tion by including reciprocating expansion engine. The Dutch Physicist Kamerlingh
Onnes finally liquefied helium in 1908. Thus, by the beginning of twentieth century
the door had been opened to a strange new world of experimentation [1–5].
The word ‘cryogenics’ comes from the Greek word ‘kryos’, which means cold.
Cryogenics is simply the science of study of materials at low temperatures at which
the properties of materials significantly change. Cold treatments were reported to
have beneficial effects on tool performance as far back as 1937. Both in the United
States and Europe, several reports have appeared of substantial benefits which can be
realized by treating steel tools at a low temperature, around 77 K. Within the United
States, claims for improvements have been expanded to include copper (Cu), car-
bides, nylon and some high temperature alloys [6]. It has been found that a cryogenic
treatment of high speed steel (HSS) allowed the use of higher cutting speed in certain
instances [7]. Gordon and Cohen [8] found that only by including a cold treatment in
the processing cycle of tool steel, a certain favorable combination of properties could
be achieved. Moderate to large improvements in tool steel performance because of
cold treatments were reported after several years later [9]. Transformation of retained
austenite at low temperatures in tool steels is expected to be dependent only on tem-
perature and not on time. But Barron [10] found that holding at for longer times
produced greater improvement in wear resistance.
On the basis of a survey of 47 companies, Smol’nikov and Kossovich [11] ob-
served that tool life was increased only about 10–40% by cryogenic treatment. Those
improvements occurred only when the tools were improperly heat treated initially.
Cryogenic technology has experienced fast development within the last few years.
The science of heat treatment is well known to each one while the principle of cryo-
genics is still a mystery to most of the people in industry. Cryogenic technique is the
treatment of the materials at very low temperature. It uses temperature around 77 K
because this temperature is easily obtainable with liquid nitrogen. Among different
means of cooling liquid nitrogen is relatively inexpensive. There is some evidence
to indicate that some of the desirable changes happen very near to this temperature,
as these changes do not happen at higher temperature. There is also some evidence
to indicate that some of changes happen as the component is within certain tem-
perature ranges on the way down to low temperature and some on the way back to
room temperature. This makes the ramp up and ramp down parts of cryogenic process
important [12]. An experimental measurement of on-resistances and switching char-
acteristics of the Metal Oxide Semiconductor Field-Effect Transistors (MOSFET)
at 77 K, 173 K, 243 K and 295 K was carried out by applying cryogenic cooling
techniques. The decrease in on-resistance and capacitance associated with the tem-
perature led to an enhancement of overall time response of the MOSFET. Decrease of
the internal thermal resistance is another advantage associated with operating MOS-
FET under cryogenic temperature [13]. Tungsten carbide cutting tools are now in
common use in industry. The differences in tool performance between cryogenically
treated and untreated tungsten carbide tool inserts during the high-speed milling of
medium carbon steel were analyzed. It has been found that cryogenically treated
tools exhibit better tool wear resistance than untreated ones. It is also evident that the
936 J Low Temp Phys (2010) 158: 934–945
application of coolant during cutting helps to reduce tool wear experienced by the
cryogenically treated tools even further [14]. Very few papers have been published
about the beneficial uses of a deep cryogenic treatment at 77 K on the properties of
high speed steel [15]. The effects of thermal shocks on flexural modulus of thermally
and cryogenically conditioned Kevlar/epoxy composites have been studied. Thermal
and cryogenic conditions were concurrently followed by down-thermal shock (pos-
itive to negative temperature excursion) and up-thermal shock (negative to positive
temperature excursion) treatments respectively on the composite laminates [16]. The
effects of thermal and cryogenic conditionings on mechanical behavior of thermally
shocked glass fiber-epoxy composites were studied by Ray [17]. The de-bonding ef-
fect of different natures of thermal shock (up and down-cycles) and strengthening
phenomena of thermal conditionings (above and subzero temperature conditionings)
were assessed for the different durations of conditioning and different states of ther-
mal conditionings (thermal and cryogenic). The state of the interactions between fiber
and polymer matrix by the treatment was reflected in the shear values of the com-
posites. Cryogenic processing of semiconductor material has been used for enhanc-
ing the Schottky contact performance for metal/InP, InGaAs contacts [18–20]. Three
methods were performed to achieve uniform tensile deformation in a nanostructured
metal. In second method, deformation is conducted at cryogenic temperature. Due to
suppressed dynamic recovery, the material regains the ability to work hardened. As a
result, uniform elongation is achieved together with an elevated strength at 77 K [21].
There are few reports on the fatigue properties of A5083 welds at cryogenic tem-
perature [22–24]. Al–Si alloys are widely used for applications in the tribological
components of I.C. engines due to their high corrosion resistance, low density and
good castability. The wear resistance of such alloys depends upon the alloy compo-
sition, applied load and sliding speed [25]. Poor seizure resistance of Al–Si alloys
tends to restrict their uses in such tribological environments [26]. The effect of deep
cryogenic treatment (DCT) on mechanical properties of tool steels through field test
and lab test on AISI M2 and AISI H13 was studied by Molinary [27]. Cold treatment
was done at 213 K to 193 K to improve surface hardness and thermal stability and
DCT was done at 148 K to 77 K, which improves properties beyond the improvement
obtained by normal cold treatment. Cryogenic treatment is an extension of conven-
tional heat treatment, which converts retained austenite to martensite. Due to this,
durability of the component was increased [28]. Collins and Dormer studied the ef-
fect of DCT on D2 cold work tool steel. Cryogenically treated samples give lowest
wear rate compared to conventional heat treated steels [29–31]. However, there were
reports from metallurgists who were doubter about cryogenic treatment [32, 33].
Reitz and Pendray [34] have reviewed the effects of cryoprocessing on steel and
some copper alloys. An improvement in wear resistance, electrical and thermal con-
ductivity, dimensional stability and hardness has been resulted. In cryogenic treat-
ment, vapors from liquid nitrogen can be used to strengthening wear parts, band saw
blades, brake rotors and pads and shear blades has been successfully cryogenically
treated by Reid [35].
Various workers have done research in the field of grinding with cryogenic coolant.
Chattopadhyay et al. [36] observed some benefits of cryogenic process with respect to
grinding forces and surface quality. The work done by Evans [37] and Bhattacharya
J Low Temp Phys (2010) 158: 934–945 937
2 Cryogenic Processing
74 hours depending upon the type and weight of material under treatment. Cryogen-
ics involves slow cooling of the material from room temperature to 77 K and ramp
down times are in the 4 to 10 hours range. Thereafter the material is soaked or holded
at 77 K for 20 to 30 hours which depends upon the volume of the part. Finally the
material is brought back to room temperature [7]. The ramp up times can be from 10
to 20 hours range.
Cryogenic is the treatment of materials at extremely low temperatures and con-
sidered to be environment friendly. Sub-zero treatments for ferrite steels at tempera-
ture of approximately 193 K transforms retained austenite left by the heat treatments
process to martensite [48] enhance the material properties. Cryogenic refines and
stabilizes the crystal lattice structure and distribute carbon particles throughout the
material resulting a stronger and hence more durable material.
All of the individual constituents that make up an alloy are placed into their most
stable state. These constituents then are aligned optimally with surroundings. Also,
molecular bonds are strengthened by the process. Particle alignment and grain refine-
ment combine to relieve internal stresses, which can contribute to part failure. This
results in material that is optimized for durability. The extremely low temperature
during cryogenic processing also slows the movement at atomic levels and increases
the internal molecular bonding energy and hence promotes a pure structural balance
throughout the material (Fig. 2). As a result the material is obtained with an extremely
uniform, refined and dense microstructure which ultimately leads to improvement in
physical and mechanical properties.
Comparative microphotographs of steel samples (Fig. 3) show the change in mi-
crostructure produced by the cryogenic treatment [49]. Smith [50] has disclosed the
apparatus and method for the deep cryogenic treatment of materials such as metal-
lic carbides, ceramics and plastics parts to materially increase their wear, abrasion,
erosion and corrosion resistivity, stabilize their strength characteristics, improve their
machinability and provide stress relief.
denser molecular structure of the metals and alloys resulting in a larger contact sur-
face area that reduces friction, heat and wear. It improves the entire structure of metals
and alloys, not just the surface. Cryo-processing is the expensive so it is employed
for the expensive machine parts and in case where the reliability of whole machine is
crucial [30].
Cryogenically treated nonferrous metals will exhibit longer wear and more dura-
bility. This growing field of engineering is an excellent technique to improve the
mechanical properties of metals. Leskovsek et al. [51] has studied the effect of deep
cryogenic processing at 77 K on wear resistance of vacuum heat treated high speed
steel (HSS). They have compared the wear resistance behavior of a vacuum heat
treated ESR AISI M2 HSS and the same vacuum heat treated steel in conjugation
with deep cryogenic processing. Deep cryogenic treated samples have a better wear
resistance than the vacuum heat treated samples, which is a result of their fracture
toughness and hardness. With increase in tempering temperature, there is increase
in wear resistance. Scanning electron microscopy (SEM) analysis of deep cryogenic
treated samples shows that their worn surfaces are less damaged in comparison to
vacuum heat treated samples.
By changing the heat-treatment conditions, it is possible to improve the strength
and resistant to creep of nickel-based alloys. The effect of heat treatment is a very
useful tool to investigate the measurement of the specific heat capacity of nickel-
based alloys. The specific heat capacity of nickel-based alloys were measured using a
differential scanning calorimetry (DSC) in the temperature range of 100–1000 K and
it increases monotonically with temperature; however, above 800 K, it is strongly
dependent on the heat treatment conditions [52]. Sorokina et al. [53] have studied
the structure and properties of nickel alloys for cryogenic applications. It is neces-
sary to have high plasticity at aging temperatures to ensure fairly high resistance
of weldments to cracking during heating of precipitation-hardening alloys. At room
and cryogenic temperatures, the toughness of nickel, stainless, and complex alloyed
martensitic steels can be increased by stabilizing austenite in a dispersed state [54].
Fatigue properties are considered to be more readily affected by the blowholes at
cryogenic temperature. Welds in Al alloys are more likely to produce blowholes and
this is one of the defects as compared with other metals. The effect of blowholes on
the mechanical properties depends upon the size, number, shape and distribution of
blowholes, as reported by Yuri et al. [55] that blowholes decreased the high cycle
fatigue properties of SUS304L weld metals particularly below 77 K. Yuri et al. [56]
have studied the effect of welding structure on high cycle and low cycle fatigue prop-
erties for metal inert gas welded A5083 Al alloys at cryogenic temperatures. They
have reported that fatigue lives of A5183 weld metals were slightly shorter than
those of A5083 base metals at cryogenic temperature, in case of low cycle fatigue
tests. Whereas, the effect of blowholes on high cycle fatigue properties are not clear.
In the low cycle fatigue tests, the fatigue lives of A5183 weld metals at 4 K were
superior to those of conventional A5083 weld metals.
Cryogenic processing is efficient in increasing the Schottky barrier height and sig-
nificantly reducing device reverse leakage current [14, 57, 58]. He and Siewenie [59]
have studied the cryogenic processing of thin metal films. Schottky barrier height was
found to be high as 0.64 eV in case of Ag/InGaAs/InP contacts fabricated by a low
940 J Low Temp Phys (2010) 158: 934–945
temperature processing. Whereas, half of this value of the same contact is obtained in
case of room temperature processing. The effect of deep cryogenic processing on mi-
crostructure, hardening behavior and abrasion resistance for high chromium cast iron
subjected to sub-critical treatments by X-ray diffraction, hardness tests and abrasion
tests were investigated by Liu et al. [60]. The results show that cryogenic processing
effectively reduces the austenite content after sub-critical treatments but can’t make
retained austenite transforms to martensite completely. Deep cryogenic processing
after sub-critical treatments can effectively boost hardness and abrasion resistance of
high chromium. The amount of precipitated secondary carbides was more than that in
air cooling and the secondary hardening peak advanced at lower temperature in case
of cryogenic processing after sub-critical treatments. Abrasion resistance reaches the
maximal when there was about 20% retained austenite in microstructures. Cryogenic
processing of surface channel diamond field-effect transistors was investigated. The
metal-insulator-semiconductor operates effectively at 4.4 K. The field effect can de-
velop the carrier concentration in less activated diamond surface channel at 4.4 K
[61].
Cryogenic processing increases the abrasion resistance to a great extent and con-
tact fatigue resistance of some metals and alloys. Singh et al. [7] have investigated
the effect of cryogenic treatment on the axial fatigue performance of fillet welded
cruciform joints of AISI 304L stainless steel, which failed in weld metals. Cryo-
genic treated samples showed the improvement in fatigue properties. Results showed
a marked increase between treated and non-treated welds and support the observa-
tion of a change in microstructure is due to cryogenic treatment. The formation of
strain-induced martensite after cryogenic treatment was confirmed by the increase in
magnetic readings in the treated samples. The yield strength, ultimate tensile strength
and elongation values for both treated and untreated cases are reported and it is clear
that tensile properties do not change due to cryogenic treatment.
The effect of cryogenic cooling by liquid nitrogen jet on forces, temperature and
surface residual stresses in grinding steels have been reviewed by Paul and Chattopad-
hyay [62]. Cryogenic cooling provide significant improvement to grinding forces,
specific gravity requirements and surface residual stresses mainly due to substantial
reduction in grinding zone temperature. It has substantially reduced the grinding zone
temperature and kept the temperature well below the critical temperature range for
steels and also reduces the magnitude of the tensile residual stress for all the mate-
rials. Cryogenic cooling has substantially more beneficial for those steels which are
quite soft, ductile and sticky.
The effects of cryogenic treatment on the H solubility and the Curie temperature of
Fe-B based glasses have been obtained. After holding the samples at cryogenic tem-
perature, the decrease in H solubility was noticed by measuring the time dependence
of pressure change in a hermetically closed chamber. This treatment also caused a
systematic lowering of temperature of the amorphous phase [63]. The Curie temper-
ature can be altered by holding the samples at cryogenic temperature and sign and
magnitude depends upon the alloy composition. The sign and magnitude can also be
influenced by the rate of liquid quench applied during the ribbon formation. Curie
temperature is lowered during cryogenic treatment for the binary Fe-B glass. The
same effect is obtained when small amount of Si is added to Fe-B glass [64]. Kim
J Low Temp Phys (2010) 158: 934–945 941
landfill. Cryogenic milling has a significant role in producing useful polymers from
the floatables. Srinivas and Jed [67] have studied the processing and properties of
cryogenically milled post-consumer mixed plastic waste stream consisting primarily
of polypropylene and polythene. Tensile properties of milled powder samples were
found to be higher in spite the presence of porosity than those of un-milled polymers.
Cryogenic mechanical alloying is an alternative strategy for the recycling of plastics.
A number of methods have been used by workers to pulverize the mixed polymer.
High energy impact conditions in a cryogenic ball milling pulverize the mixed plas-
tics into a powder. Ball milling was carried out at cryogenic temperatures by using
liquid nitrogen [68].
The cryogenic liquid gas cooled the reactant plastic mixture in the liquid state and
provides granulation or pulverization by cold shock. The problem of multiple sur-
face cracking in glass fiber reinforced plastics as a result of thermal shock at a low
temperature was studied by Sei [69]. The order of stress singularity around the tip of
the crack has been obtained in the case of crack that ends at the interface between
orthotropic elastic materials. Takeda et al. [70] have studied the stress intensity fac-
tors for woven glass/epoxy laminates with cracks at cryogenic temperature. For the
case where crack is normal to and ends at an interface between two fiber bundles,
the order of stress singularities at the tip of a crack is obtained. To determine the
stress intensity factors at crack tip of two layered woven laminates, they used finite
element methods and presented the results in graphical form. Yamanaka et al. [71]
have developed the fiber reinforced plastics expanding by cooling down to low tem-
perature. High strength polyethylene is used as strengthening fiber. They explained
the applications of fiber reinforced plastics to winding frames and spacers of a su-
per conducting coil. It has been resulted that fiber reinforced plastics with negative
expansion property, high thermal conductivity and low friction co-efficient is useful
in the super conducting field. The X-ray scattering, DSC and transmission electron
microscopy (TEM) techniques were used to study the effect of cryogenic mechani-
cal milling on the structure and the thermal behavior of isotactic polypropylene. The
structural changes by mechanically milling are only partly reversible. DSC results
showed the decrease in degree of crystallinity with increase in milling time which is
attributed to a reversible transformation of the initial morphology in to nanostructured
morphology [72]. Fritz et al. [73] has studied the effect of cryogenics on rapid pro-
totyping materials. They apply cryogenics processing to photopolymer epoxy resins
as well as to stratasys’ acrylonitrile butadiene styrene (ABS) thermoplastic material.
They hope an improvement in wear resistance, abrasive resistance, fatigue resistance
and reduction in internal stresses. Cryogenic processing may make the materials less
brittle without affecting the hardness.
brought about by plastic flow of the matrix. Levi and Papazian [75] used the
thermo-elastoplastic finite element methods to investigate the thermal cycling of
silicon carbide whisker reinforced Al-matrix composites (SiC/5456). They ob-
tained the changes in residual quantities during thermal cycling including cy-
cling to cryogenic temperatures and the effect of these changes on subsequent
mechanical behavior. Mao et al. [76] produce TiAl/NiAl intermetallic compos-
ites by using cryogenic mechanical alloying products. They evaluate the mechan-
ical properties by small punch testing and through micro-indentation measure-
ment. Consolidated composites showed exceptionally high hardness values, which
are attributed to the formation of ternary phases at the temperatures of consolida-
tion. The samples consolidated at high temperature possessed low fracture tough-
ness which is also attributed to the formation of ternary phases during consolida-
tion.
Hemanth [77] prepared B4 Cp/Al-12%Si composites in which Al-12% Si alloy
was the matrix and boron carbide particles (B4 Cp) were the reinforcing material.
The characterization of tribological behavior of cryo-chilled Al-B4 C composites cast
using high rate heat transfer during solidification was studied. He observed that mi-
crostructures of the chilled composites are finer than that of the un-chilled matrix
alloy with uniform distribution of B4 C particles. Strength, hardness and wear resis-
tance of the chilled metal matrix composites (MMC) also found better to those of
the matrix alloy. Chilled MMC showed mild wear regime with high coefficient of
friction at lower load but at higher loads MMC showed severe wear with better wear
resistance than the matrix alloy.
Because of high specific strength and stiffness and low electrical and thermal con-
ductivity of glass fiber reinforced composites, these are attractive alternatives to met-
als for cryogenic applications. Disdier et al. [78] found that glass fiber reinforced
epoxy composites can be used effectively for cryogenic applications using a vacuum
as thermal insulation. Glass fiber reinforced composites were subjected to various
cure cycles and subsequently cryogenically cooled and influence of polymer chemical
composition and processing parameters on the magnitude of residual stress developed
in these composites has been reported. Significant differences in residual interfacial
strain were produced by different resin systems. The polyester resin developed a very
low residual interfacial strain which suggest that this type of material should perform
well in cryogenic applications [79].
6 Conclusion
Cryogenic processing is the treatment of the materials at very low temperature around
77 K. This technique improves the physical and mechanical properties of the materi-
als. Cryogenic refines and stabilizes crystal lattice structure and distribute carbon par-
ticles throughout the material resulting a stronger and hence more durable material.
Cryogenic treated metals and alloys will exhibit more wear resistance and more dura-
bility. Plastics become stronger and durable and composites showed better strength,
hardness and wear resistance than the pure matrix alloy.
944 J Low Temp Phys (2010) 158: 934–945
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