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Elevated-pressure mixed-coolants JouleThomson cryocooling

B.-Z. Maytal
*
,1
, G.F. Nellis, S.A. Klein, J.M. Pfotenhauer
The University of Wisconsin-Madison, Madison, WI 53706, USA
Received 3 November 2005; accepted 8 November 2005
Abstract
This paper explores the potential of mixed coolants at elevated pressures for JouleThomson cryocooling. A numerical model of a
JouleThomson cryocooler is developed that is capable of simulating operation with mixtures of up to 9 components consisting of hydro-
carbons, non-ammable halogenated refrigerants, and inert gases. The numerical model is integrated with a genetic optimization algo-
rithm, which has a high capability for convergence in an environment of discontinuities, constraints and local optima. The genetic
optimization algorithm is used to select the optimal mixture compositions that separately maximizes following two objective functions
at each elevated pressure for 80, 90 and 95 K cryocooling: the molar specic cooling capacity (the highest attainable is 3200 J/mol) and
the produced cooling capacity per thermal conductance which is a measure of the compactness of the recuperator. The optimized cooling
capacity for a non-ammable halogenated refrigerant mixture is smaller than for a hydrocarbon mixture; however, the cooling capacity
of the two types of mixtures approach one another as pressure becomes higher. The coecient of performance, the required heat transfer
area and the eect of the number of components in the mixture is investigated as a function of the pressure. It is shown that mixtures with
more components provide a higher cooling capacity but require larger recuperative heat exchangers. Optimized mixtures for 90 K cryo-
cooling have similar cooling capacity as those for 80 K. Optimized compactness for 80 K is about 50% higher than can be achieved by
pure nitrogen. For 90 K, no mixture provides a more compact recuperator than can be achieved using pure argon. The results are dis-
cussed in the context of potential applications for closed and open cycle cryocoolers.
2005 Published by Elsevier Ltd.
Keywords: JouleThomson coolers (E); Gas mixture (B); Cycle optimization (E)
1. Introduction: open and closed cycles and mixed coolants
JouleThomson cryocoolers may be classied as either
open cycle (OC) or closed cycle (CC). Initially, OC cryoco-
olers were operated using pure coolants at elevated pres-
sures. However, from the beginning the development of
OC cryocoolers was accompanied by attempts to close
the cycle [14]. The characteristics of the two categories
are very dierent. The central element of the CC cryocooler
is its compressor, which is a bulky, unreliable, an expensive
part of the system, and the source of vibrations. It is there-
fore desirable to reduce the operating pressure in a CC
cryocooler in order to alleviate these problems and also
lower the consumption of energy as characterized by an
improvement in the cycle COP (thermodynamic coecient
of performance).
The OC cryocooler is used for radiation detectors [57],
cryosurgical probes [810], and space applications [11]. The
OC cryocooler is energized by a gas reservoir which has the
function of extending the available operating period.
Therefore, elevated pressure becomes a desirable feature
of an OC cryocooler as high-pressure storage results in
more gas stored in a gas reservoir of xed volume and
therefore increased operating time. In contrast to the CC
systems, COP is not a major concern for OC systems
because the compression process does not occur at the site
of cryocooling. Another feature of OC JouleThomson
cryocooling is fast cooldown. Even if only a short run time
is required it is still necessary to use a high operating pres-
sure in order to maintain the high rate of cooldown.
0011-2275/$ - see front matter 2005 Published by Elsevier Ltd.
doi:10.1016/j.cryogenics.2005.11.005
*
Corresponding author. Tel.: +972 4908 7570; fax: +972 4990 6100.
E-mail address: benmay@rafael.co.il (B.-Z. Maytal).
1
On leave from Rafael, Ltd., P.O. Box 2250, Haifa 31021, Israel.
www.elsevier.com/locate/cryogenics
Cryogenics 46 (2006) 5567
The potential for mixed coolants to enhance Joule
Thomson cryocooling has allowed a dramatic reduction
in the operating pressure as compared with the pressure
required by traditional pure coolants in a JouleThomson
cycle. Mixed refrigerants allow ecient operation using a
single stage compression process, which provides operating
pressures that are below 2.5 MPa. Furthermore, to enable
lubrication of the compressor, the candidate mixtures are
expected to dissolve some lubricant contamination in their
liquid phase at the cryogenic temperature. Viable and gen-
eral-purpose JouleThomson closed cycle cryocoolers with
high COPs and prolonged reliable run times, driven by sin-
gle stage lubricated compressors. are currently available
[1216] both with and without phase separators [17,18].
Much less attention has been devoted to the potential of
mixed coolants in the context of OC cryocoolers. Note that
the low-pressure mixtures that have been developed for CC
operation are not applicable, in general, for high-pressure
operation as operation at elevated pressure will prevent
them from reaching the cryogenic temperatures. On the
other hand, harnessing these mixtures in an OC cryocooler
at low pressure will exhibit an unacceptably lower cooling
capacity and increase the size of the required gas reservoir.
There are several reported studies on OC cryocooling
with mixtures at elevated pressure. At the moderate pres-
sure range of 10 MPa, Brodianski et al. [19] demonstrated
experimentally the potential of mixtures to gain accelerated
cooldown. Brodianski demonstrated cooldown times with
mixtures that were eight times faster than could be
achieved using pure nitrogen at a similar volumetric ow
rate and pressure. Boiarski et al. [20] describes an experi-
ment with an open cycle regulated cryocooler fed through
two pressure vessels, each at 6.2 MPa to utilize the mixing
enthalpy. Chorowski [21] discussed open cycle operation
with mixtures of nitrogen with methane and nitrogen with
R-13 at pressures up to 14 MPa. Gong et al. [22] discussed
the use of nitrogen and hydrocarbon mixtures for acceler-
ating cooldown of open cycle JouleThomson cryocoolers.
Only a single analysis at higher pressures (up to 30 MPa)
has been reported: Maytal et al. [23] show how the cooling
capacity of a three component mixture can be optimized.
Little [24] used a 30 MPa mixed precoolant to accelerate
the cooldown of a nal nitrogen stage.
1
2 3
4
5
recuperator
evaporator
throttle
heat
load
gas
reservoir
or
compressor
high, operating
pressure
0.1 MPa

Q
P

Fig. 1. Layout and notation of the simulated JouleThomson cryocooling


system.
Nomenclature
A heat transfer area (m
2
)
COP coecient of performance
COP
C
coecient of performance of the reversible cycle
of Carnot
h specic enthalpy (J/kmol)
Dh
T
integral isothermal JouleThomson eect, (J/
kmol)
Dh
T,PP
value of Dh
T
at T
PP
(J/kmol)
_ n molar ow rate (kmol/s)
NTU number of thermal units, U A= _ n c
P

P pressure (Pa)
P
OP
pressure at which a mixture was optimized (Pa)
s specic entropy (J/kmol K)
T temperature (K)
T
AMB
ambient temperature, gas inlet temperature (K)
T
B
normal boiling point (K)
T
M
melting/solidication temperature (K)
T
OP
ambient temperature at which a mixture was
optimized (K)
DT
PP
minimum temperature dierence along the recu-
perator (K)
Q total amount of rejected heat at the cryocooling
temperature (J)
_
Q cooling capacity, heat load (W)
_
Q
REC
recuperated enthalpy (W)
V volume of a gas reservoir (m
3
)
U overall heat transfer coecient (W/m
2
K)
_
W minimum compressing power (W)
y
i
molar fraction of component i
Subscripts
1 to 5 states along the thermodynamic cycle, Fig. 1
i index of any component in mixture
j index of the sections along the recuperator in the
numerical model
I number of components in mixture
H high (pressure or temperature) stream
L low (pressure or temperature) stream
OP state at which a mixture was optimized
Greek
q density (kmol/m
3
)
Abbreviations
min
y
(x) minimum value of (x) while changing parameter
y
OC open cycle
CC closed cycle
OM optimal mixture
56 B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567
Longsworth [25] employed binary mixtures of nitrogen
and argon at 40 MPa for open cycle fast cooldown. How-
ever, these two components have similar boiling points
and therefore no thermodynamic advantage is expected.
Indeed the operating temperatures and rates of cooling
were intermediate between the values that could be
attained using either of the two pure components.
The intended contribution of the present study is an
investigation of the potential of mixed coolants to improve
the performance of high-pressure OC cryocooler applica-
tions at 80, 90 and 95 K as alternatives for nitrogen and
argon.
2. The model, optimization procedure and tools
The layout and notation associated with the modeled
JouleThomson cryocooler are indicated in Fig. 1. The
cryocooler includes a recuperative heat exchanger, throttle
(constant enthalpy expansion), and the evaporator (or load
heat exchanger). A numerical model using the Engineering
Equation Solver software [26] was developed to simulate
the steady state operation of this cycle. The details of the
numerical model are described elsewhere [27] in the context
of optimization of a low-pressure mixture composition.
The thermophysical properties of the components and their
mixtures were obtained using the NIST4 numerical code,
also known as SUPERTRAPP [28]. Up to 9 component
mixtures can be considered with constituents that include
various hydrocarbons, halo-carbonated refrigerants, and
inert gases.
The total recuperated enthalpy,
_
Q
REC
_ n
h
1
h
2
h
5
h
4
1
is carried in N equal parts by each section, j, along the
recuperator.
The heat load supported by the evaporator,
_
Q
_ n
h
4
h
3
2
matches the cooling capacity of the cycle which is the min-
imum departure between the low- and high-pressure iso-
bars in the Th plane at the temperature range, (T
B
, T
AMB
),
_
Q
_ n
min
T
hP
L
; T hP
H
; T min
T
Dh
T
Dh
T;PP
3
The allowable minimum temperature dierence (the pinch-
point temperature dierence), DT
PP
, is an input parameter
to the model which reects the nite real nature of the lim-
ited area recuperative heat exchanger,
DT
PP
minT
H
T
C
4
The required heat transfer area or thermal conductance
(U A)
j
of the jth section may be determined using the eec-
tivenessNTU relationship for a counter ow heat exchan-
ger. Other input parameters to the model include: the inlet
pressure and temperature of the mixture at state 1, (P
1
, T
1
),
the molar ow rate, _ n, the temperature of cryocooling, T
4
,
the species and their fractions, y
i
, and the outlet pressure,
P
5
, which was assumed to be 0.1 MPa for all of the results
presented here.
The minimum compressing power (corresponding to a
reversible and isothermal compression process) is,
_
W
min
_ n
T
1
s
5
s
1
h
5
h
1
5
which enables one to obtain the maximum possible coe-
cient of performance,
COP
_
Q
_
W
min
6
The solution for the temperature proles along the recu-
perator is obtained iteratively by adjusting the hot temper-
ature dierence, T
1
T
5
until the specied pinch-point
temperature dierence is achieved. For pure coolants, the
pinch-point occurs at the hot end and therefore the hot
temperature dierence coincides with DT
PP
.
The numerical model is integrated with a genetic opti-
mizing algorithm [29] implemented in Engineering Equa-
tion Solver that is characterized by a high capability for
nding the global optima of a target function even if the
function and/or its derivatives and constraints are non-
continuous. The genetic optimization algorithm is not
confused by local optima and converges to the global
one.
The scope of optimization is to maximize one of three
target functions: the cooling capacity, the coecient of per-
formance, or the compactness of the recuperator,
_
Q=U A. Computations are repeated after adjusting the
composition by the genetic optimizer for further improve-
ment of the objective function. Results are generated for
dierent values of: (a) high pressure, (b) number of species,
(c) ambient temperatures, and (c) cryocooling temperatures
(either 80 or 90 K).
The domain of the optimized-mixture compositions is
restricted by considerations of solidliquid equilibrium in
order to avoid clog formation at the throttle. A conserva-
tive approach was adapted in this regard; the freezing tem-
perature of the mixture, T
M
, was estimated according to
T
M
6
X
I
i1
y
i
T
M;i
7
and the choice of components for 80 K cryocooling was
restricted so that,
T
M
6 T
B
nitrogen 8
On the one hand, some rise of the boiling point of the mix-
ture may be expected, even if it is relatively small and re-
mains in the 80 K cryocooling range. On the other hand,
even a small presence of nitrogen, like a few percent, is ade-
quate for the mixture to reach the boiling point of nitrogen
B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567 57
[30]. The condition guaranteeing a non-clogging operation
then is
T
3
PT
M
9
The optimized mixtures for 90 K cryocooling still employ a
substantial fraction of nitrogen as the lowest boiling point
specie. Therefore, their throttle exit remains at the same
temperature and the restriction (8) remains valid.
Optimizing the composition for maximum
_
Q= _ n may be
accomplished entirely in the Th plane. However, the inte-
gration along the recuperator serves to determine its size
and therefore allows optimization of the composition for
the most compact heat exchanger.
3. Specic cooling capacity
3.1. General scope
Two types of mixtures were examined for cryocooling at
80 K. The components of the rst type of mixtures are
mainly hydrocarbons and are selected from group I as
listed in Table 1. The second type of mixture contains
mostly halogenated derivatives of hydrocarbons which
are selected from group II listed in Table 1. Mixtures of
the rst type (group I components) are ammable whereas
mixtures of the second type (group II components) are not.
The composition of each mixture was optimized at a spe-
cic pressure, P
OP
, for maximum specic cooling capacity,
_
Q= _ n.
The lowest boiling point component for either of the
two groups is nitrogen. The components have to be chosen
so that their normal boiling points will be uniformly dis-
tributed over the entire temperature range from 80 to
300 K so that the occurrence of a pinch-point at some
intermediate temperature might be avoided; the pinch-
point constitutes the bottleneck (literarily, in the Th plan)
that xes the value of
_
Q= _ n that can be obtained. This
discussion is consistent with Littles [31] formulation of
the optimal mixture, namely, equidistant high and low-
pressure isobars in the Th plan.
The contribution of each additional component
becomes more signicant as its involvement bisects and
narrows a larger gap between the boiling points of other
components. Therefore, CF
4
, a non-ammable component,
is included in group I to narrow the wide gap (73 K)
between methane and ethane. Mostitski et al. [32] com-
mented in 1981 on the possibility of improving the e-
ciency of hydrocarbon mixtures by employing the
component CF
4
. Luo et al. [33,34] discussed the benet
of including CF
4
in comparison to mixtures of hydrocar-
bons only. Sometimes acetylene, C
2
H
4
, is also included in
order to bridge the gap between methane and propane
[35,36]. A dierent reason motivates the presence of argon
in the mixture. Argon has a signicantly larger integral
JouleThomson eect, Dh
T
, than nitrogen, in spite of hav-
ing a similar boiling point.
3.2. Hydrocarbon mixtures
Mixtures were optimized in which all 9 components in
group I were allowed. In addition, 3, 6, 7 and 8 component
mixtures were considered in which only some of the con-
stituents listed in group I were considered. The heat rejec-
tion temperature used for the optimization, T
OP
, was 290 K
for cryocooling at 80 K. The optimized
_
Q= _ n as a function
of the corresponding P
OP
are displayed in Fig. 2. Each
curve belongs to a specic group of components. These
curves do not describe a single mixture since each of the
points on a given curve represents a dierent composition
that is optimal for the specic pressure. Therefore, each
curve may be regarded as corresponding to a virtual cool-
ant that is referred to as the Optimized Mixture (OM) given
a set of components and operating condition. This view-
point is analogous to the pure coolants pressure dependent
Dh
T
(at ambient or inlet temperature) which reects the
highest attainable
_
Q= _ n. Note that Fig. 2 illustrates the cool-
Table 1
Two groups of candidate components to comprise optimized mixtures: the
hydrocarbons (I) and the halogenated hydrocarbons (II)
Group I T
B
[K] Group II T
B
[K]
Nitrogen N
2
77.2 N
2
77.2
Argon Ar 87.3 Ar 87.3
Methane CH
4
111.7 CH
4
111.7
R14 CF
4
145.1 CF
4
145.
Acetylene C
2
H
4
169.1 R23 190.0
Ethane C
2
H
6
184.5 R116 194.7
Propane C
3
H
8
231.2 R32 221.2
Isobutane C
4
H
10
263 R125 224.7
Isopentane C
5
H
12
300.6 R134a 246.8
0 10 20 30 40 50
0
500
1000
1500
2000
2500
3000
methane
7
6
3A
3B
8
argon
nitrogen
3C
9


Q n
J mol
290 K =
AMB
T
80 K
cryocooling
methane
7
6
3A
3B
8
argon
nitrogen
3C
9
[ ]
OP
P [MPa]
Fig. 2. Optimized specic cooling capacity of various hydrocarbon
mixtures (OM curves) as a function of the pressure of optimization. Each
curve indication represents the mixture by the number of its components.
Nitrogen, argon, and methane are shown for reference. (9) N
2
, A, CH
4
,
CF
4
, C
2
H
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
, C
5
H
12
; (8) like 9 without C
2
H
4
; (7) like 8
without CF
4
; (6) like 7 without C
5
H
12
; (3A) N
2
, C
2
H
6
, C
3
H
8
; (3B) N
2
,
C
3
H
8
, C
4
H
10
; (3C) N
2
, CH
4
, C
2
H
6
.
58 B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567
ing capacity,
_
Q= _ n , as a function of a mixtures optimiza-
tion pressure, P
OP
, but not the operating pressure, P.
Therefore it does not describe the cooling capacity
achieved during a discharge process of a gas reservoir.
Fig. 2 includes for reference the
_
Q= _ n (which is equivalent
to the Dh
T
(P)) for nitrogen, argon and methane. The com-
position of these pure refrigerants does not change with
pressure and therefore these are the corresponding dis-
charge curves. The use of nitrogen, argon, and methane
are appropriate for cryocooling at about 78 K, 88 K and
112 K, respectively. Note that the optimized mixtures have
higher
_
Q= _ n than argon at any pressure and even higher
than methane below 20 MPa.
Any optimized mixture that is obtained from a larger
group of components that contains as its basis a smaller
group of components must perform better than the original
mixture obtained from the smaller group. In other words,
the 9 component OM in Fig. 2 must perform better than
the 8 component OM which, in turn, must perform better
than the 7 component OM and so on. The reason is that
at any pressure, the domain of optimization of the original
OM is entirely included in the domain of the mixtures of
more components. Put another way, the optimization pro-
cedure always has the option to abandon the additional
components of the larger group, by reducing their molar
concentration, if necessary in order to obtain a larger
_
Q= _ n. Indeed, Fig. 2 shows that the various OM curves do
not intersect and the one with most components will exhi-
bit the highest
_
Q= _ n.
Synthesizing mixtures of 8 components with boiling
points distributed quite evenly along the entire range of
temperatures from 80 to 300 K provides the condence
that the optimization procedure does not require any
additional and intermediate components for further
enhancement of
_
Q= _ n. Therefore,
_
Q= _ n of this OM is
expected to be the envelope that encompasses any possible
hydrocarbon mixture or at least a very good approxima-
tion of this envelope. Indeed, Fig. 2 shows that the inclu-
sion of a 9th component, which in this case is C
2
H
4
, does
not elevate the performance noticeably at any optimization
pressure even though its boiling point bisects the 40 K gap
that otherwise exists between CF
4
and C
2
H
6
.
As observed in Fig. 2, the
_
Q= _ n curves of the OM exhibit
a peaking behavior with pressure that is similar to the Dh
T
of pure gases. However, the peak occurs at lower pressures
and is not related to the inversion of the JouleThomson
eect. The peaking pressure associated with the 8 compo-
nent OM clearly designates the highest attainable cooling
capacity,
_
Q= _ n, that can be achieved by any mixture at
any pressure. The highest value of
_
Q= _ n observed in this
study is 3180 J/mol for a heat rejection temperature of
290 K. The corresponding peak pressure is about 20 MPa
and its composition is listed in Table 2 (together with opti-
mized compositions at 10 and 40 MPa). However, notice
that the peak is relatively shallow and a cooling capacity
of nearly 93% of this optimal value may be reached at
7 MPa; albeit using a mixture with a dierent composition.
For nitrogen at a similar cryocooling temperature, the
cooling capacity
_
Q= _ n is 1200 J/mol at about 40 MPa and
for argon it is 1800 J/mol at 55 MPa.
The three component mixtures N
2
C
2
H
6
C
3
H
8
and
N
2
C
3
H
8
C
4
H
10
develop maximum
_
Q= _ n of about 2620
J/mol and 2430 correspondingly, which is more than twice
that of pure nitrogen; these results are consistent with the
optimized peaking values obtained by Maytal et al. [23].
The mixture N
2
CH
4
C
2
H
6
reaches 2520 J/mol at about
45 MPa. Six components bring
_
Q= _ n closer to the envelope
represented by the 8 component OM and achieves a peak
cooling capacity of 2960 J/mol. There is essentially no dif-
ference in performance exhibited by the 7 and 8 component
OM in the high-pressure region, however the addition of
the 8th component (which is CF
4
) does improve
_
Q= _ n at
lower pressures.
The 7 and 8 component OMs are partially condensed at
the elevated pressures and the discussed temperature of
290 K which means at the inlet to the recuperator. How-
ever, the gas phase mass fraction is at least 90%. The pos-
sibility of enjoying higher
_
Q= _ n and COP by allowing a
coolant to stay in two-phase outside the recuperator was
previously mentioned in the literature in the context of
low-pressure mixtures for CC cryocoolers. Alexeev et al.
[15,37] and Boyarski et al. [38,39] compared the perfor-
mance of the two classes of Gas Refrigerant Supply
(GRS) and Liquid Refrigerant Supply (LRS). On the other
Table 2
Composition of mixtures (percent mole fractions) of 8 hydrocarbon components optimized at three values of P
OP
= 10, 20 and 40 MPa at 290 K for
maximum
_
Q= _ n
P [MPa]
_
Q= _ n [J/mol] N
2
A CH
4
CF
4
C
2
H
6
C
3
H
8
C
4
H
10
C
5
H
12
1.5 1464 54.1 3.4 10.5 12.1 5.2 5.2 0.0 9.5
3 2171 55.2 0.2 7.6 13.7 13.3 0.7 0.0 9.3
5 2751 60.4 0.1 5.0 11.1 11.6 0.8 3.0 8.0
7 2947 61.2 4.3 5.0 5.5 11.4 2.1 3.8 6.7
10 3080 64.6 2.0 9.8 1.7 9.0 5.0 0.6 7.3
20 3180 70.2 2.3 8.6 1.3 7.2 2.2 1.2 7.0
30 3070 74.6 0.0 7.4 2.5 6.2 2.0 1.0 6.3
40 2930 75.5 2.3 6.0 2.6 4.7 2.1 1.7 5.1
The highest attainable
_
Q= _ n value occurs at 20 MPa.
B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567 59
hand, the ow of the two-phase might be heterogeneous
and therefore the performance will be aected by the
details in this ow regime.
The liqueed part of the 7 component OM includes a
substantial portion of the higher boiling point component,
which is isopentane. This component was removed for the
6 component OM and therefore the 6 component OM is
more likely to be in a single phase at the elevated pressure.
Notice that the performance of the 6 component OM is
only slightly worse than the 7, 8, or 9 component OM.
For instance, the 7 components OM at 20 MPa and
30 MPa, both at 290 K, are of two phases. Their gas phase
mass fractions are 90% and 97.5% correspondingly. On the
other hand, the 6 components OM at 25 MPa and 290 K is
of single phase. This mixture is mentioned in Section 10.1
for comparison and its composition is displayed in Table
5, optimized for 80 K cryocooling.
The composition of the OMs at elevated pressures, nom-
inally above 5 MPa, are not aected by the melting point
restriction and thus strongly fulll the inequality repre-
sented by Eq. (8). However, at lower pressures, this melting
point restriction becomes constraining and the optimized
compositions are on the boundary of this restriction and
Eq. (8) is fullled as an equality. The melting point restric-
tion therefore limits the share of higher boiling point com-
ponents in the mixture which in general also have higher
values of T
M
and Dh
T
[40]. Therefore, it might be that
the optimized
_
Q= _ n is underestimated at low pressures and
the actual values may be higher if the suppression of the
solidication point of the blend were accurately accounted
for. However, this issue was already discussed for low-pres-
sure mixtures for CC cryocoolers [23,41] and is not the
focus of the present study. Even though Table 2 displays
some compositions of OM at the lower pressure range gen-
erated by this study.
3.3. Halogenated hydrocarbon mixtures
The results of optimizing
_
Q= _ n for mixtures based on the
halogenated hydrocarbon refrigerants summarized as
group II in Table 1 are displayed in Fig. 3. The values of
_
Q= _ n for these OMs are smaller than can be achieved using
hydrocarbon components from group I (the 8 component
hydrocarbon envelope previously shown in Fig. 2 is also
shown in Fig. 3). The shortfall in performance is particu-
larly true in the low and intermediate pressure range; how-
ever, the performance of the halogenated hydrocarbons
approaches that of the hydrocarbons at pressures above
35 MPa.
The boiling points of the halogenated hydrocarbon
components are distributed less uniformly than those of
the hydrocarbons. Therefore, the inclusion of the 9th com-
ponent which is (the ammable) methane in order to nar-
row the 57 K boiling points gap between argon and R14
does somewhat enhance
_
Q= _ n at elevated pressures. At
50 MPa, the value of about 2500 J/mol for halogenated
hydrocarbon only becomes 2600 J/mol when including
methane. Another obstacle is the higher T
M
value that is
typical of the components in group II which causes these
OMs to be on the border of the solidication constraint
represented by Eq. (8) for most of the optimization pres-
sures. Consequently, it is not possible to include higher
boiling point components as much as would otherwise be
optimal from the standpoint of enhancing
_
Q= _ n. Refriger-
ants that are currently banned, such as R12, R13 and
R21, or an alternative substitute that has a similarly lower
T
M
value would close the gap between the OM based on
hydrocarbons and the synthetic refrigerants. The synthetic
refrigerant OM also exhibits a peaking behavior; the larg-
est
_
Q= _ n occurs at 35 MPa and the associated composition
is listed in Table 3 together with two other synthetic
OMs that are optimized at 20 and 45 MPa.
4. Coecient of performance of optimized mixtures
The COP at elevated pressure is another reection of the
improved cooling capacity of the OM. The COP as a func-
tion of optimization pressure is shown in Fig. 4 for mix-
tures optimized from the same groups of components
that are employed from the hydrocarbon category (group
I in Table 1) and discussed in the previous section in the
context of Fig. 2. The OMs with more components and
higher
_
Q= _ n also exhibit higher COP and the COP shows
the same peaking behavior with respect to pressure. How-
ever, the pressure associated with the highest COP is some-
what lower than the peak pressure associated with; this
behavior is similar to pure gases as discussed by Mann
et al. [42]. The curve associated with the 8 component
OM again represents an envelope that encompasses the
performance associated with other, partial groups of com-
ponents. This envelope has the signicance of representing
0 10 20 30 40 50
0
500
1000
1500
2000
2500
3000


Q n
[ ] J mol
290 K =
AMB
T
80 K
cryocooling
OP
P [MPa]
argon
nitrogen
8-HC
3-HC
8-HH
Fig. 3. Optimized specic cooling capacity of halogenated hydrocarbon
mixtures (OM curves) as a function of the pressure of optimization. For
reference are shown hydrocarbon mixtures, nitrogen and argon. Each
curve indication represents the mixture by the number of its components.
(8-HH) N
2
, A, R14, R23, R32, R134a, R116 and R125; (8-HC) N
2
, A,
CH
4
, CF
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
, C
5
H
12
; (3-HC) N
2
, C
2
H
6
, C
3
H
8
.
60 B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567
the highest achievable COP with a JT cycle with any mix-
ture at any pressure; Fig. 4 shows that for a heat rejection
temperature of 290 K, the maximum COP is 0.19 which is
50% of the COP that can be achieved by a reversible
Carnot cycle, COP
C
. The maximum COP is achieved at
an optimization pressure of only 5 MPa by a mixture of
a composition that is listed in Table 4 and includes about
60% nitrogen. One may compare it with the composition
of the mixture that optimizes
_
Q= _ n (which peaks at
20 MPa) that includes 70% nitrogen (Table 2). The peak
COP associated with pure nitrogen is about 0.07 and this
peak is reached at about 30 MPa. For argon 0.11 is the
peak COP which is achieved at about 40 MPa. Therefore,
not only is the COP of the OM doubled in comparison with
a pure substance but it is also achieved at one eighth of the
pressure. The halogenated hydrocarbon mixtures reach a
maximum COP of about 0.14 at a pressure of 32 MPa
for the same 290 K heat rejection temperature and 80 K
cryocooling temperature.
An alternative attempt was made to optimize directly
the COP (instead of the cooling capacity) as an objective
function for each pressure and it was found that the same
composition that maximizes
_
Q= _ n also maximizes the COP.
This result may be explained by the extremely weak depen-
dence of the compression work on the composition of the
mixture.
5. Temperature eect on optimized mixtures
The T
AMB
, of an operating mixture has to be considered
in reference to the temperature for which it was optimized,
T
OP
. There are three aspects associated with the inuence
of temperature on
_
Q= _ n for an OM. In general, the inuence
of ambient temperature becomes more sensitive at lower
pressures.
5.1.
_
Q= _ n dependence on T
OP
As the temperature for which the optimization is per-
formed, T
OP
, is raised,
_
Q= _ n degrades quite moderately.
Fig. 5 shows the 7 component OM, optimized at 290 and
at 333 K; these curves represent dierent mixtures as the
optimization conditions for each are dierent. At elevated
pressures, above 10 MPa, the dierence between the two
curves remains within 15%. The optimization procedure
compensates for the higher temperature by changing the
composition so that the concentration of the higher boiling
point components is increased. Therefore, it is possible to
optimize a mixture for operation at elevated temperature
with a relatively small sacrice of
_
Q= _ n.
5.2.
_
Q= _ n dependence on T
AMB
when T
AMB
> T
OP
The most evident situation is when T
AMB
= T
OP
(for
example, the curves where T
AMB
= T
OP
= 290 K and
T
AMB
= T
OP
= 333 K) so that the OM operates at the
Table 4
Composition (percent mole fractions) of 8 components optimized mixture that exhibits the peaking COP value of 0.19 at 290 K reached at the pressure of
5 MPa
N
2
A CH
4
CF
4
C
2
H
6
C
3
H
8
C
4
H
10
C
5
H
12
60.4 0.1 5.0 11.1 11.6 0.8 3.0 8.0
0 10 20 30 40 50
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
7
8
nitrogen argon
6
3A
3B
3C
COP
OP
P [MPa]
290 K =
AMB
T
80 K
cryocooling
7
8
nitrogen argon
6
3A
3B
3C
Fig. 4. Coecients of performance as a function of the pressure of
optimization (OM curves). The various hydrocarbon mixtures were
optimized for highest
_
Q= _ n. Each curve indication represents the mixture
by the number of its components. Nitrogen and argon are shown for
reference. (8) N
2
, A, CH
4
, CF
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
, C
5
H
12
; (7) like 8
without CF
4
; (6) like 7 without C
5
H
12
; (3A) N
2
, C
2
H
6
, C
3
H
8
; (3B) N
2
,
C
3
H
8
, C
4
H
10
; (3C) N
2
, CH
4
, C
2
H
6
.
Table 3
Composition (percent mole fractions) of mixtures of 8 halogenated hydrocarbon components optimized at 3 values of P
OP
= 20, 35 and 45 MPa at 290 K
for maximum
_
Q= _ n
P [MPa]
_
Q= _ n [J/mol] N
2
A R14 R23 R116 R32 R125 R134a
20 2260 76.0 0.0 0.0 18.7 0.0 4.2 0.5 0.6
35 2700 73.5 3.6 7.9 6.6 0.2 3.8 0.5 3.9
45 2550 81.1 0.2 6.1 2.0 1.5 0.0 2.3 6.8
The highest attainable
_
Q= _ n value occurs at 35 MPa.
B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567 61
temperature that it was optimized for. However, practically
the mixture must operate over a range of ambient temper-
atures that might be higher than T
OP
. Fig. 5 shows mix-
tures which were optimized at room temperature,
T
OP
= 290 K, but operate at an ambient temperature of
60 C so that T
AMB
= 333 K. In this case, the sensitivity
to the higher ambient temperature is much more pro-
nounced than if the mixture was optimized for operation
at 333 K (i.e., the performance for the OM with
T
AMB
= 333 K and T
OP
= 290 K is signicantly less than
the OM with T
AMB
= 333 and T
OP
= 333 K). The reduc-
tion in performance associated with operation at 333 K is
more than doubled at 50 MPa as compared with the
previous case where the mixture is optimized for high-
temperature operation; the reduction in performance is
even more dramatic below 30 MPa. Note that the local,
non-smooth behavior marked by X in Fig. 5 is not
expected but remains even when the components CF
4
and C
2
H
4
are added to the mixture.
5.3.
_
Q= _ n dependence on T
AMB
when T
AMB
< T
OP
Operation at an ambient temperature below the optimi-
zation temperature for an OM is not accompanied with a
signicant gain in
_
Q= _ n as it would be for a pure gas; instead,
the cooling capacity remains almost the same for any oper-
ating temperature T
AMB
that is below. Since optimized mix-
tures have two equidistant isobars of low and high pressure
in the Th plane, the case of lower T
AMB
is described by the
same isobars and the same separation in the h direction.
This separation denes
_
Q= _ n and therefore, in principle,
the cooling capacity should remain unchanged. However,
practically, the optimization process is not absolutely per-
fect and the two isobars are not completely equidistant.
For instance, the 7 component mixture that is optimized
at 20 MPa and T
OP
= 333 K exhibits
_
Q= _ n 2897 J/mol
when it is operated at 333 K. When the same OM is oper-
ated at lower temperatures, T
AMB
= 300, 290, 260, 240,
220 K, the corresponding calculated
_
Q= _ n values are 2866,
2872, 2865, 2872 and 2875 J/mol. These values are close
to the optimized value, 2897 J/mol, within 0.41%. The
small deviations reect the well-optimized nature of that
particular composition.
Based on this discussion, a reasonable strategy is to opti-
mize the mixed coolant for the highest probable operating
temperature, T
AMB
. The associated
_
Q= _ n will be somewhat
lower than the largest attainable, however, it will remain
almost the same value over the entire range of lower T
AMB
.
6. Recuperator sizing for optimized mixtures
The
_
Q= _ n values of previously discussed OMs were ideal
in the sense of fully utilizing an unlimited heat transfer
area. In order to obtain the required heat transfer area
associated with the various OMs, a minimum temperature
dierence between the recuperating streams of DT
PP
= 3 K
is assumed. The numerical model determines for each step
the required amount of thermal conductance and normal-
izes this thermal conductance, (U A)
j
against the local
minimum average capacity rate, _ n c
P;j
where,
c
P;j
minc
P;H
; c
P;L
10
In this way, the corresponding non-dimensional element of
heat exchanger size is expressed in terms of the Number of
Transfer Units, NTU
j
, for each element. The summation
of these local number of transfer units provides the total
NTU of the entire recuperator
NTU
X
N
j1
U A
j
_ n c
P;j
11
Fig. 6 displays the pressure dependence of the NTU de-
manded by some of the OMs with the same groups of com-
ponents that were previously discussed in comparison to
that of pure nitrogen and argon. In general, mixed coolants
even at elevated pressure are more demanding in terms of
NTU than pure nitrogen. This observation has been dis-
cussed elsewhere in the context of low-pressure mixtures
for CC cryocoolers [43]. The more ecient OMs in terms
of
_
Q= _ n and COP have more components and therefore pro-
vide a lower average temperature dierence between the
recuperating streams. This characteristic necessitates larger
overall thermal conductance, U A and therefore the asso-
ciated NTU becomes higher.
However, the physical sizes of the recuperators for
mixed coolants and pure nitrogen cannot be compared
on the basis of NTU. A signicant portion of both chan-
nels of mixed coolant recuperator includes two phase ow
while for nitrogen (and other pure gases) both channels
carry a single phase which is gas. The heat transfer coe-
cient in the former case is associated with boiling and
may be signicantly larger (by a factor of 23) than of pure
nitrogen. This counter aspect tends to reduce the physical
0 5 10 15 20 25 30 35 40 45 50
0
500
1000
1500
2000
2500
3000
argon
333 K
290 K
333 K
nitrogen
Q n
[ ] J mol
OP
T
333 K
290 K
333 K
290 K
333 K
X
80 K
cryocooling
290 K
AMB
T
0 5 10 15 20 25 30 35 40 45 50
0
500
1000
1500
2000
2500
3000
argon
333 K
290 K
333 K
nitrogen
[ ]
OP
P [MPa]
X
T
Fig. 5. The aect of elevating the temperature of optimization, T
OP
, and
the ambient temperature, T
AMB
, on cooling capacity as a function of the
pressure of optimization (OM curves) for 7 component mixtures. The
mixtures were optimized for highest
_
Q= _ n and include the 7 components,
N
2
, A, CH
4
, C
2
H
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
, C
5
H
12
.
62 B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567
size of the mixed coolant recuperator thus narrowing the
dierence between the physical sizes of the two.
7. Open cycle application
7.1. Discharge process of a reservoir
High-pressure coolants are traditionally applied to OC
cryocooler systems where a gas reservoir discharges
through the JouleThomson cryocooler. If the discharge
process occurs slowly, then the gas reservoir may be
regarded as isothermal during this process. As previously
discussed, the cooling capacity
_
Q= _ n as a function of pres-
sure for the 6 component OM of group I, as is shown in
Fig. 7, is not a description of a discharge process; each
point along this curve represents a dierent mixture com-
position. Fig. 7 shows the discharge process associated with
5 of these OMs for which the pressure of optimization,
P
OP
, is 50, 40, 35, 30 and 25 MPa; these curves are gener-
ated assuming an isothermal discharge process and the
instantaneous
_
Q= _ n are displayed as a function of pressure.
Each of these mixtures may also be examined at a higher
pressure than the one for which it was optimized. Note that
the values of
_
Q= _ n at any pressure dierent from the optimi-
zation pressure must lie below the envelope of OM. Fig. 7
shows the pressure dependence above and below P
OP
for
P
OP
= 25 MPa (only a short portion of the curve at higher
pressure is shown in order to avoid unnecessarily compli-
cating the gure).
The proper criteria for comparing the performance of a
mixture for an OC cryocooler would be the total refrigera-
tion provided at the payload, Q, per unit volume of the res-
ervoir. The ow demand is assumed to be ideal in the sense
of instantaneously matching the specic cooling capacity
and heat load (as described elsewhere [44] for pure cool-
ants) then,
Q
V

Z
P
F
P
I
Dh
T;PP
dq 12
from the initial high pressure, P
I
to the nal one, P
F
. To
accomplish this integration, one would need the density
dependence of
_
Q= _ n during the isothermal discharge pro-
cess, as shown in Fig. 8 for the same ve optimized mix-
tures that were previously described. Fig. 8 also shows
the P
OP
= 25 MPa OM at P > P
OP
. The area below these
curves represents the Q/V values for the various coolants.
The curve of P
OP
= 50 MPa exhibits some uctuations as
0 10 20 30 40 50
0
10
20
30
40
50
NTU
OP
P [MPa]
290 K =
AMB
T 80 K cryocooling
argon
nitrogen
8-HC
6-HC
3-HC
8-HH
=
PP
T 3K
290 K =
AMB
T
8-HC
6-HC
3-HC
8-HH
=
PP
T 3 K
Fig. 6. The required sizes of recuperators performing with DT
PP
= 3 K, as
a function of the pressure of optimization (OM curves). The mixtures were
optimized for highest
_
Q= _ n. Each curve indication represents the mixture by
the number of its components. Nitrogen and argon are shown for
reference. (8-HC) N
2
, A, CH
4
, CF
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
, C
5
H
12
; (6-HC)
like 8-HC without CF
4
and C
5
H
12
(3-HC) N
2
, C
2
H
6
, C
3
H
8
; (HH) N
2
, A,
R14, R23, R32, R134a, R116 and R125.
0 10 20 30 40 50
0
500
1000
1500
2000
2500
3000
Q n
[ ] J mol
Optimized mixtures
discharge
25 30
35
40
50 MPa
argon
nitrogen
290 K =
AMB
T
80 K
cryocooling
curves
OP
P
50 MPa

P [MPa]
Fig. 7. Cooling capacity pressure dependence during isothermal discharge
process. The mixtures were optimized for highest
_
Q= _ n and include the 6
components: N
2
, A, CH
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
: the dashed line for
P
OP
= 25 MPa is extended for P > P
OP
.
0 2 4 6 8 10 12 14 16 18
500
1000
1500
2000
2500
3000
Q n
[ ] J mol
Optimized mixtures
[ ] J mol
25
30
40
50 MPa
20
5
7
10
argon
nitrogen
80 K
cryocooling
10
290 K =
AMB
T
50
30
50
OP
P
discharge
curves
0 2 4 6 8 10 12 14 16 18
500
1000
1500
2000
2500
3000
Q n
[ ] J mol
[ ] J mol
50 MPa
10
290 K =
AMB
T

Fig. 8. Cooling capacity density dependence during isothermal discharge


process. The mixtures were optimized for highest
_
Q= _ n and include the 6
components: N
2
, A, CH
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
: the dashed line for
P
OP
= 25 MPa is extended for P > P
OP
.
B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567 63
a function of q although the curve is smooth when shown
as a function of P; this seems to reect a diculty with the
numerical properties correlations rather than any real
behavior.
7.2. Examples
The OM for P
OP
= 40 MPa remains single phase in the
gas reservoir while discharging from P
OP
to 5 MPa. The
integral shown in Eq. (12) shows that this mixture provides
a gas reservoir volume specic refrigeration capacity of Q/
V = 22.1 kJ/L. Pure nitrogen for the same pressure range
discharge can provide only 10 kJ/L Furthermore, the cut
o pressure for pure nitrogen at a similar heat load would
be about 10 MPa (because of the lower specic cooling
capacity) therefore, the Q/V would be reduced to only
8.8 kJ/L.
The OM associated with P
OP
= 35 MPa becomes two
phase below about 11 MPa; this pressure may therefore
be considered to be the practical limit to the nal pressure
of the discharge process. Even so, the Q/V integral for the
OM associated with 35 MPa is 18 kJ/L from 35 MPa to
11 MPa, which is more than twice that of nitrogen at
40 MPa.
The OM associated with P
OP
= 50 MPa discharging
from a reservoir from 50 MPa to 10 MPa can provide Q/
V as high as 25 kJ/L. Nitrogen at the same pressure range
provides only 11.3 kJ/L.
Indeed, Q/V increases for higher P
OP
mixtures in the
case where the reservoir is assumed to be charged initially
to P
OP
. However, a gas reservoir may be charged to a
higher pressure than P
OP
in which case each of the OMs
shown in Fig. 8 have similar Q/V integrals. In this case,
the OMs with higher P
OP
are more likely to stay single
phase during the discharge process.
8. Closed cycle application
The
_
Q= _ n of OM of group I (Fig. 2) increase quite shar-
ply up to pressures of about 10 MPa where they have
achieved most of the cooling capacity that is possible,
about 3000 J/mol and close to 50% of COP
C
. This strong
pressure dependence at low pressures is characterized by
a slope of about 400 J/mol per 1 MPa. (The pressure
dependence for pure nitrogen is only 50 J/mol per
1 MPa). The strong pressure dependence encourages
designers to double or triple the pressure of a CC cryoco-
oler to about 2 or 3 MPa. This pressure increase would
require adding a single compression stage while remaining
in a moderate pressure range (below 10 MPa) but still
enjoy values of
_
Q= _ n and COP that are nearly equal to the
maximum attainable. This remains consistent with pub-
lished performance data [45] for CC cryocoolers at 2 and
5 MPa achieving
_
Q= _ n of about 5001000 J/mol and COP
of 2030% of COP
C
. The practice of using two stages of
compression was reported with pure nitrogen [46], hydro-
carbon mixtures [47] and synthetic refrigerants [48].
The COP and
_
Q= _ n of OMs do peak at dierent pressures
and therefore occur for dierent compositions. Operation
at the highest COP (which occurs at 5 MPa) is associated
with giving up about 15% of the highest attainable
_
Q= _ n
(which occurs at about 20 MPa). One may try to compro-
mise between these two working points by choosing an
intermediate pressure and composition.
9. Minimum size recuperator
In some applications, the main concern is to minimize
the size of the recuperator even if this means sacricing
_
Q= _ n. Such an example may be the miniature cryosurgical
probe [27,49,50] or any other case where the platform of
the cold end is very delicate.
9.1. Pure coolants
While maintaining a constant ow rate, one may make
the size of a the recuperator progressively smaller in terms
of its thermal conductance, U A so that it becomes more
compact; this reduction in conductance is associated with
some loss eectiveness and thus in
_
Q= _ n. The question as
to whether and to what extent this strategy pays o is
examined by the parameter of compactness,which is,
_
Q=U A, and has units of degrees Kelvin. Since
_
Q and
U A are proportional to _ n, their ratio is independent of
_ n and characterizes the recuperator itself. A larger
_
Q=U A represents a more compact heat exchanger as a
given cooling rate is produced by a smaller recuperator.
Fig. 9 illustrates the compactness parameter,
_
Q=U A
for pure nitrogen at 40 MPa and 290 K as a function of
the NTU. Note that initially, the cooling capacity
_
Q
decreases more slowly than U A therefore
_
Q=U A
increases. However, if U A becomes too small then
_
Q
2 3 4 5 6 7 8 9 10 11
0
1
2
3
4
5
6
7
8
NTU
40
40
35
35
30
30
25
25
20
20
15
15
10
10
5
5
3
3
PP
T =
PP
T =
Q

optimized
mixtures
nitrogen
290 K =
AMB
T
80 K
cryocooling
40 MPa
NTU
40
40
35
35
30
30
25
25
20
20
15
15
10
10
5
5
3
3
PP
T =
PP
T
U A
290 K =
AMB
T
Fig. 9. Optimized compactness parameter, as a function of the size of the
recuperator, for 7 component hydrocarbon mixtures including N
2
, A,
CH
4
, C
2
H
6
, C
3
H
8
, C
4
H
10
, C
5
H
12
in comparison to that of nitrogen. The
DT
PP
values for each size recuperator are noted along the curves.
64 B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567
sharply decays and dominating
_
Q=U A which drastically
decreases. The maximum value of
_
Q=U A for nitrogen is
5.05 K and is obtained with a recuperator sized by an NTU
value of 5.5. The numbers along the curves in Fig. 9, from 3
to 40 K, represent the warm end temperature dierence
between the recuperating streams which is also the DT
PP
for pure nitrogen. For smaller recuperators, as NTU
decreases, DT
PP
grows and is accompanied by a growing
gap between the actual specic cooling capacity,
_
Q= _ n,
and the potential or ideal one, Dh
T
. The peak value of
_
Q=U A is associated with a DT
PP
of about 16 K and at
this point
_
Q= _ n is 781 J/mol which is still about 65% of Dh
T
.
9.2. Mixed coolants
Can the use of mixtures at elevated pressure make the
recuperator more compact? In order to explore the highest
attainable
_
Q=U A and the associated composition, the
following procedure was adapted. At a given pressure,
for any value of DT
PP
the numerical model was used to
optimize the composition of a 7 component mixture com-
posed of group I hydrocarbons in order to directly maxi-
mize the compactness factor
_
Q=U A. Increasing DT
PP
values from 3 to 40 K is accompanied by further reduction
of recuperator size. Similar to pure nitrogen, the
_
Q=U A
value for these optimized mixtures exhibits a peak value
that is shown in Fig. 9. It should be claried that each
locally optimized point along this curve and its associated
composition namely, maximizing
_
Q=U A while imposing
a DT
PP
value, does not have any specic signicance since
by letting larger DT
PP
the optimized
_
Q=U A may
increase. However, these points pave the road to the global
optimum, which is the peaking point of this curve.
At the same conditions of 40 MPa and 290 K, the high-
est value of the compactness factor is 7.1 K at a DT
PP
between 20 and 30 K and NTU of about 4. This is about
50% more compact than nitrogen and it occurs at a smaller
NTU. The composition at the peaking
_
Q=U A is about
70% of nitrogen with the remaining 25% made up of argon
and the rest of the hydrocarbons. The
_
Q= _ n is about 1120 J/
mol which is only about 1/3 of the maximum attainable
value by mixtures (when optimized for
_
Q= _ n and similar
to the highest value attainable for pure nitrogen under
the same conditions. This procedure was repeated for 30
and 50 MPa and the peak value of
_
Q=U A were found
to be smaller than for the 40 MPa shown in Fig. 9.
Longsworth [51] considered the compactness of recuper-
ators when operated with pure coolants and proposed the
parameter, Dh
T
=
_
Q
REC
= _ n, which is indeed,
_
Q=
_
Q
REC
.
Dobak and Radebaugh [49,50] modied this parameter
for mixtures so that it becomes Dh
T;PP
=
_
Q
REC
= _ n. This
parameter can be used to compare coolants based on their
potential to tolerate a smaller recuperator while operating
at very high eectiveness. It is derived solely through the
thermophysical properties and in the Th plane. However,
it cannot serve to determine absolute gures of required
NTU, as in the case of operation at low eectiveness, to
gain additional compactness.
10. Mixtures for 90 and 95 K
10.1. Cooling capacity
Components of hydrocarbons group (I) and haloge-
nated hydrocarbons group (II) (Table 1) were optimized
for maximum
_
Q= _ n while cryocooling at the somewhat ele-
vated temperature of 90 and 95 K. The resulting
_
Q= _ n values
are only slightly higher than was obtained for the OM for
80 K. The gain by tolerating 90 K or even 95 K instead of
80 K is minor and therefore one may deduce that there are
no OMs for 90 and 95 K. Equivalently, one may state that
OMs for 80 K are approximately the same as the OMs for
90 and 95 K as observed in Table 5 which summarizes the
OM composition as a function of cryocooling temperature.
The situation is similar for mixtures of halogenated
hydrocarbons. For instance, the optimized mixture for
90 K at 35 MPa has
_
Q= _ n of 2775 J/mol whereas when it
is optimized at 80 K (Table 3) it has
_
Q= _ n 2700 J/mol.
Radebaugh discussed [52] how much entropy is enough
for cryocooling at any temperature. In this sense, the
entropy of the 90 K OM is mainly assigned around 80 K
and, consequently, the temperature of absorbing the heat
load will vary from 78 K to 90 or 95 K.
The 90 K OM still contains more than 60% nitrogen and
less than 8% argon. The low concentration of argon may be
explained by its high T
M
and by the fact that the major
enhancement of
_
Q= _ n is due to the hydrocarbons.
While optimized mixtures for 80 K cryocooling were
compared with nitrogen, the mixtures optimized for 90 K
must be compared with argon. However, the small gain
at 90 K on the one hand, and the special position of argon
as a noble gas and thus a superior coolant for JouleThom-
son cryocooling [53], on the other, do somewhat attenuate
the benet associated with using a mixed-gas coolant. For
instance, let us compare with argon the optimized mixture
at 50 MPa, 290 K for 90 K cryocooling. Indeed the
_
Q= _ n is
2850 J/mol against 2100 for argon. However, while dis-
charging down to 10 MPa, the mixtures provide Q/V of
Table 5
Compositions (percent mole fractions) of optimized mixtures at 30 MPa, 290 K for cryocooling at 80, 90 and 95 K
T [K]
_
Q= _ n [J/mol] N
2
A CH
4
C
2
H
6
C
3
H
8
C
4
H
10
C
5
H
12
80 3072 70.5 5.6 8.7 5.2 2.6 1.3 6.1
90 3115 65.1 6.1 14.5 4.9 1.3 2.1 6.0
95 3229 62.1 7.6 15.1 5.7 1.2 2.4 5.9
B.-Z. Maytal et al. / Cryogenics 46 (2006) 5567 65
about 26.5 kJ/L while argon at similar conditions provides
21.8 kJ/L. Argon compensates its lower
_
Q= _ n by higher
density at elevated pressure (Fig. 8) so that its Q/V inte-
gral approaches that of the optimized mixtures to within
20%.
10.2. Recuperators compactness
The optimization of mixtures for maximum compact-
ness parameter,
_
Q=U A, for cryocooling at 90 K points
to pure argon as the best choice. In analogy to the discus-
sion for 80 K cryocooling in Section 9, at 40 MPa, and
290 K the highest value of
_
Q=U A for argon is 25.2 K.
It is more then three times larger than for the optimized
mixtures for 80 K. However, one should still recall that
argon cools down to 90 K instead of 80 K. The associated
_
Q= _ n is 1050 J/mol which is about 50% of the highest attain-
able value by pure argon.
This characteristic might explain the use of high pres-
sure, open cycle argon for miniature cryosurgical probes
[54,55]. In the view of the compactness analysis, the mixed
coolant probes for similar cryocooling temperature cannot
be as compact as that of argon at elevated pressure. Still
mixed coolants are used for cryosurgical probes [56,57]
though at higher cryocooling temperatures and lower
pressures.
Acknowledgement
This work was partially sponsored by the Oce of
Naval Research under contract N00014-03-1-0175.
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