Int. J. Refrig. Vol. 19, No. 8, pp.

485-496, 1996
, ~'t ~,,~ Copyright © 1996 Published by Elsevier Science Ltd and IIR
~il
ELSEVIER PII: S0140-7007(96)00008-4
Printed in Great Britain. All rights reserved
0140-7007/96/$15.00

REVIEW PAPER
Working fluids for mechanical refrigeration - Invited paper
presented at the 19th International Congress of Refrigeration,
The Hague, August 1995
A l b e r t o Cavallini
I s t i t u t o di Fisica T e c n i c a , via Venezia 1, Universit~t, I 35131 P a d o v a , I t a l y
Received f o r publication 9 February 1996

The phasing out of fully halogenated halocarbons becomes effective at the end of 1995 by international
agreement. Under the same ozone depletion issue, the companion fluids HCFCs are suffering a similar fate,
as they are considered controlled substances with a virtual phase-out by 2020, and more drastic reductions
may be proposed in the near future. Some international action might also be agreed upon on refrigerants
with regard to the threatened environmental emergency of anthropogenic global warming. Therefore, in
choosing replacement fluids primary concern must be given to minimising the total warming impact, which,
for most applications, calls'for improved energy efficiency. During recent years, industry has scrutinised and
proposed a number of new synthesised products as immediate drop-in or long-term replacements for fluids
harmful to the environment. Together with some single-component new generation refrigerants, quite a few
two-component, three-component or even four-component mixtures, both with zeotropic and azeotropic
behaviour, are being considered. The main issues associated with the use of the new generation refrigerants
are discussed, such as behaviour with oil; flammability; efficient use of temperature glides, fractionation and
heat-transfer degradation with zeotropic mixtures. The full environmentally friendly option of resorting to
natural fluids is also considered by examining some recent innovative applications as refrigerants of some
hydrocarbons, ammonia, carbon dioxide, water and air. Copyright © 1996 Published by Elsevier Science
Ltd and IIR
(Keywords:mechanicalrefrigeration;workingfluids;refrigerants)

Fluides de travail pour le froid m6canique - Rapport

pr6sent6 au 19e Congr6s International du Froid,
La Haye aofit 1995
L'~limination progressive des halocarbures totalement halog~n~s est devenue effective it la fin de 1995 sur
accord international. L 'appauvrissement de la stratosphere en ozone, fait subir le m~me sort it tous les fluides de
type HCFC, dont on pr~voit l'~limination pratiquement complbte pour 2020 et qui risquent des limitations
encore plus radicales. Une action relative aux frigorig~nes pourrait dtre conclue au plan international, eu ~gard
it la menace grandissante que fait peser sur l'environment le r~chauffement de la planbte dfi it l'activit~ humaine.
Par consequent, le souci de minimiser l'impact total sur le r~chauffement doit presider au choix des fluides de
remplacement, ce qui, dans la plupart des applications, n~cessite d'am~liorer les performances ~nerg~tiques. Au
cours des dernibres ann~es, les industriels ont ~tudi~ et proposk un certain nombre de nouveaux produits de
synth~se comme produits de remplacement imm~diat ou it long terrne des fluides nuisibles it l'environnement.
Sont actuellement it l'~tude, en m~me temps que les frigorig~nes purs, d'assez nombreux mdlanges it deux, trois
ou quatre composants, azdotropes aussi bien que non-az~otropes. Les principales questions associ~es it
l'utilisation de nouveaux frigorigbnes sont it l'dtude, comme le comportement avec l'huile, l'inflammabilit~, ainsi
que l'utilisation efficace des glissements de temperature, la s~paration et la ddgradation du transfert de chaleur
avec les mdlanges z~otropes. Le recours it desfluides naturels, les plus recherch~s au titre de l'environnement, est
~galement examin~ it travers les rdcentes innovations en matibre d'applications de frigorigbnes tels que certains
hydrocarbures, l'ammoniac, le dioxyde de carbone, l'eau et l'air.

The end of 1995 marked a turning-point for the
refrigerant substitution process; it involved the phas-
ing-out of fully halogenated halocarbons, known as
CFCs, by international agreement between all developed
countries, while developing countries benefited from a
more relaxed phase-out schedule.
The partly halogenated companion products H C F C s ,
regarded within the Montreal Protocol scenario as
necessary transition fluids, are nevertheless destined to
a similar fate under the same ozone depletion issue. The
Copenhagen and Vienna amendments to the Montreal
Protocol established H C F C s as controlled substances
with a phase-out in new equipment by the year 2020, and
at the 9th meeting in Montreal in autumn 1997, the
parties adhering to the Protocol might approve a more
accelerated phase-out schedule.

485
486
household refrigeration
retail refrig.(current losses)
retail refrig.(reduced losses)
commercial chillers
unitary air conditioners
autom.a.c.(current losses)
autom.a.c.(reduced losses)
0 10
Figure l Relative proportion of direct/indirect effects to TEWI for selected refrigeration applications of HCFC and H F C alternatives (ITH = 100
years)
Figure 1 Proportion des effets directs/indirects sur le T E W I de produits de remplacement de H C F C et H F C (horizon - 100 ans) pour les applications
suivantes
Since December 1993, EU Ministers for environment
protection have agreed upon earlier HCFC phase-out
dates, with a total ban by the end of 2014. Individual
countries have imposed much tighter restrictions; for
example in Sweden the phasing-out of HCFCs in new
equipment has been set for the beginning of 1998, while
in Germany the phase-out of HCFC22 in new equipment
will be in force from the beginning of the year 2000.
Austria too set a tighter HCFC phase-out schedule than
that of the EU (HCFC phase-out date as refrigerant
in new equipment will be in force from the beginning
of 2002).
In Switzerland, all HCFCs will be banned by 2005 and
in New Zealand by 2015, while, in the USA, selected
HCFCs are scheduled to undergo an early phase-out;
HCFC22 elimination from new equipment has been set
for 2010, and that of HCFC123 for 2020, while
HCFC141b production and consumption will be
banned as from 2003. For export-oriented companies it
is most disturbing that regulations on HCFC phase-out
are so different from country to country, and subject to
frequent and unpredictable updates.
As seen, the ozone issue has resulted in well-
established international action, with the complete
ban of all ozone-harmful compounds within a few
years. This same action (especially the CFC ban), can
also greatly benefit the other, perhaps even more
threatening, environmental emergency of our times:
that of anthropogenic global warming, for which a
specific, international agreement has not so far been
established. Nevertheless, in the preparatory meetings
for the assembly of the parties involved in the United
Nations Framework Convention on Climate Change
(Rio Convention) some pressure has been placed on the
setting of restrictions in the use of trace greenhouse
gases, which of course include non-chlorinated halo-
carbons HFCs, now considered the most promising
candidates for long-term replacement of CFCs and
HCFCs on the basis of their harmlessness to the
stratospheric ozone layer.
It will no doubt be a difficult task for policymakers to
make general decisions on refrigerant regulations in
A. Cavallini
nn
---n
f
20 30 40 50 60 70 80 90 100
%
compliance with the global warming issue. It is a well-
known fact that to determine the overall contribution of
refrigerants to global warming, a systematic approach
has to be employed taking into account both the direct
contribution of the working fluid as a greenhouse gas
and the indirect contribution of carbon dioxide emission
resulting from the production of the energy required to
operate the equipment throughout its normal life. For
this purpose, GWP (Global Warming Potential) indices
referring to CO2 have been determined to provide a
simplified means for describing the relative influence of
each greenhouse gas emission on future radiative
forcing and thereby direct effect on the global climate.
These indices are calculated from a cumulative
radiative forcing over a suitable Integration Time
Horizon, ITH.
In the evaluation of the indirect contribution to the
Total Equivalent Warming Impact (TEWI) of
electrically powered equipment, due consideration has
to be given to the global warming impact of the local
power-generation plant that depends on the resource
energy mix used and on electric-power generation,
transmission and distribution efficiency. Emissions of
CO2 due to electricity generation can vary considerably
from one country to another. Regional average values
are 0.51 kg CO2kWh~- l (delivered to end users) for
western Europe, 0.67 kg kWh~ 1 for North America, and
0.58 kg kWhe' for Japan.
On the basis of the above averaged data and current
technology, Figure 1 shows the relative proportion of
direct/indirect effects on TEWI for selected refrigeration
applications of HCFC and HFC alternatives, based on
an 1TH = 100 years 1. Evidently, in some applications
there may still be plenty of room for improvement in
global warming impact by moving further from the
H C F C - H F C alternative to non-GWP compounds, or
through drastic modifications of system features. Prac-
tical means to reduce refrigerant emissions into the
atmosphere, such as improving design, maintenance and
service practices to minimise leakages, or reducing
system charge and implementing refrigerant reclaiming
procedures can be pursued. This is especially true, for
 Working fluids for mechanical refrigeration
mobile air,
industrial
domestic
commercial
air
0 5
Figure 2 1986 consumption of all halogenated fluids in refrigeration and air conditioning
Figure 2 Consommation de fluides halogtn6s dans le froid et le conditionnement d'air en 1986
example, in retail refrigeration and automotive air
conditioning, both non-hermetic systems which feature
refrigerant loss rates typically of the order of 20-35% of
the total charge per year. On the other hand, very little
can be done to reduce TEWI by focusing merely on the
refrigerant in other refrigeration applications, where the
major contribution to TEWI comes from the CO2
produced for energy consumption; in these cases,
efficiency improvement offers a far greater opportunity
to reduce TEWI.
To evaluate the relative impact on anthropogenic
global warming of a refrigeration application, data in
Figure 1 is to be considered in conjunction with the
distribution of refrigerant consumption; this data is
reported in Figure 2, relative to the Montreal Protocol
reference year 1986. TEWI index is not therefore a
refrigerant property, unlike ODP or GWP, but depends
to a large extent on the particular application and
location considered. How this concept can effectively be
used in setting refrigerant regulations remains an open
question.
Alternative synthesised refrigerants
Table 1 indicates some alternative synthesised chlori-
nated refrigerants now available on the market2'3; most
of them are intended to serve as short-term, drop-in
replacements for CFCs with minor system modifi-
cations. All these alternatives are based on HCFCs;
the presence of chlorine thus ensures adequate lubricity
and solubility with traditional mineral oils and alkyl-
benzene lubricants. Furthermore, all the chlorinated
refrigerants offered as drop-in replacements for CFC 12
and R502 are in the form of zeotropic or near-azeotropic
mixtures. They are tailored to give approximately the
same performance (primarily capacity with positive
displacement compressors and energy consumption)
within the same systems as the CFCs they are replacing
(look-alike alternatives). A factor of prime impor-
tance to this goal is a close matching of the saturation
pressure-to-temperature correlation at evaporator con-
ditions. Of course, even material compatibility with
motor insulation (in hermetic systems) and elastomers
487
10 15 20 25 30 35
%
should not be overlooked when retrofitting existing
equipment.
Table 2 lists some chlorine-free alternative refriger-
ants, mostly based on HFCs; some of them have already
been introduced onto the market, while others are still
undergoing close experimentation. Several mixtures are
considered, especially as alternatives for R502 and
HCFC22, for which no non-flammable single-component
alternatives with similar pressure-temperature property
profiles have yet been found. Although some of these
mixtures have been formulated to display approximately
the same volume-refrigerating capacity in common
applications as the old-generation refrigerants they are to
substitute, strictly speaking, in no event can they be
considered as true drop-in alternatives in systems with
positive displacement compressors, owing to the fact that
they require at least substitution of the traditional
lubricants. It is a well-known fact that, due to the absence
of chlorine, both mineral oils and alkylbenzene lubricants
do not have adequate lubricity, and are not miscible with
HFC refrigerants. An intensive research effort that lasted
for several years came to the conclusion that polyol ester
oils (with proper additives) are the best choice for use
as lubricants with HFC refrigerants in almost all
applications.
A major concern regarding the use of POE lubricants
is their high hygroscopicity; with moisture levels in the
system exceeding limits of the order of 100ppm, oil
breakdown can occur, possibly bringing about copper
plating and rusting, which can seriously reduce com-
pressor life4. In centrifugal compressors the lubricant
does not come into contact with the circulating
refrigerant, and mineral oil can be the best choice also
with HFC working fluids.
Another point that should be carefully considered with
POE lubricants is their high tendency to dissolve
contaminants and manufacturing chemicals, like wire
and shell drawing lubricants, residual in the system. The
implementation of controlled procedures in processing
the equipment during manufacturing, assembly and
installation, and the use of proper filter-dryers can
avoid the possible occurrence of system failures caused
by the peculiar characteristics of POEs s.
488 A. Cavallini

Table 1 Alternative refrigerants containing HCFCs

Tableau 1 FrigorigOnes des remplacement contenant des HCFC

ASHRAE no. Composition NBP* (°C) ODP GWP* Brand

(rating) (% mass f.) (bubble/glide) (RI1 = 1) (CO2 = 1) Replacing name

R22 -40.9 0.055 1700 R502

(A1) mixture component
R 123 27.9 0.020 93 CFC 11
(B1)
R 124 - 13.2 0.022 480 CFC 114
mixture component
R141b 32.2 0.110 630 CFC11
R142b -9.1 0.065 2000 mixture component
(A2)
R401A R22/152a/124 (-33.0/6.3) 0.037 1100 CFC12 Suva TM
(A 1/A 1) (53/13/34) MP 39
R401B R22/152a/124 ( - 34.6/5.9) 0.040 1200 C FC 12 Suva TM
(A 1/A 1) (61 / 11/28) R500 MP 66
R401C R22/152a/124 (-28.3/4.7) 0.030 850 CFC 12 Suva TM
(A 1/A 1) (33/15/52) MP 52
R402A R125/290/22 (-48.9/2.0) 0.021 2600 R502 Suva TM
(A I/A 1) (60/2/38) HP 80
R402B R 125/290/22 (-47.1/2.3) 0.033 2200 R502 Suva TM
(A 1/A 1) (38/2/60) HP 81
R403A R290/22/218 ( - 50.0/2.5) 0.041 2700 t R502 Isceon TM
(A 1/A 1) (5/75/20) > 8000 § 69-S
R403B R290/22/218 (-49.5/0.9) 0.030 3700 t R502 lsceon TM
(A 1/A 1) (5/56/39) > 14000§ 69-L
R405A R22/152a/142b/C318 (-35.5/5.5) 0.028 CFC12 G2015
(A 1/A 1) (45/7/5.5/42.5)
R406A R22/600a/142b (-36.0/9.9) 0.057 1800 CFC12 G H G 12
(A1/A2) (55/4/41)
R408A R 125/143a/22 (-44.4/0.7) 0.026 3000 R502 Forane TM
(A1/AI) (7/46/47) FX 10
R 125/143a/290/22 (-45.6/1.0) 0.027 2500 R502 Meforex TM
(42/6/2/50) DI 44
R409A R22/124/142b ( - 34.3/8.5) 0.048 1400 CFC 12 Forane TM
(A1/A1) (60/25/15) FX 56
R22/124/142b ( - 35.5/7.7) 0.048 1400 CFC 12 Forane TM
(65/25/10) FX 57
R22/124/600 (-32.1/6.1) 0.038 1100 CFC12 Meforex TM
(50/47/3) DI 36
R509 R22/218 -47.5 (azeo) 0.024 4700 $ R502 Arcton TM
(A I) (44/56) > 19000§ TP5R2
R411A R1270/22/152a 0.048 1500 HCFC22 G2018A
(AI/A2) (1.5/87.5/11)
R41 IB R1270/22/152a 0.052 1600 R502 G2018B
(A1/A2) (3/94/3)
R412A R22/218/142b (-40.1/8.1) 0.055 2000 ~ R500 Arcton TM
(A1/A1) (70/5/25) >3300 § TP5R

* Boiling point or (bubble point/temperature glide) at p = 1 atm. Temperature glide: (Tae w - Tbubble )
t l T H = 100 years
~;According to ref. 28, where GWPx00 = 7000 is attributed to FC218
§According to ref. 29, where GWPI00 > 34000 is attributed to FC218
(Some ASHRAE designations or ratings are still under public review)

Another point worth mentioning is that the use of
POE lubricants with HFC refrigerants in positive
displacement compressors, as compared to the use of
previous refrigerants and mineral oil, may result in a
higher susceptibility to slugging damage under flooded
start conditions. Moreover, the noise power level emitted
by a positive displacement compressor working with
POE lubricants is somewhat higher than with mineral
oils; this seems due to a different sound absorption action
of the foamed and dispersed oil interface in the
compressor crankcase.
The use of synthesised refrigerants causes some
concern regarding possible future restrictions on the
basis of their global warming impact. This fact apart,
efforts to identify and develop suitable look-alike long-
term alternatives for CFC12 and R502 seem so far to
come up to expectation; the major question is still the
long-term reliability of equipment using HFC134a and
HFC NEARMs (NEar Azeotropic Refrigerant Mix-
tures) with the new lubricants.
The situation is somewhat different with HCFC22,
most widely used in almost all air-conditioning applica-
 Working fluids for mechanical refrigeration
HFC-32
R-410A~
"-'I°BF
/ \
HFC-125 HFC-134a
Figure
3 Flammabilityboundariesfor mixtures of HFC-32/125/134a
Figure 3 Limites d'inflamrnabilit~ des m~langes HFC-32-125/134a
tions, for which all the non-flammable look-alike
alternatives fall in the category of NARMs (Non
Azeotropic Refrigerant Mixtures) ~. With regard to this
point, the preliminary conclusions of the international
co-operative AREP program on identification and
testing of possible substitutes for HCFC22 (based on
compressor calorimeter, system drop-in and soft-
optimisation test results) can be summed up as follows:
(a) no single refrigerant which clearly outperforms all
the other possible alternatives in all types of systems
tested has emerged;
(b) there may be many viable new-generation alter-
natives which could yield performance ratings
similar to and, after extensive systems redesign,
possibly even better than HCFC22 as far as
capacity and efficiency are concerned;
(c) there are many issues still to be fully addressed
before HCFC22 can be completely abandoned,
such as fractionation of NARMs, flammability,
long-term reliability of equipment using new
refrigerants and lubricants, lubrication and heat
transfer.
Among the various non-flammable alternatives to
HCFC22 listed in Table 2, three directions seem to be
gaining most favourable support depending on applica-
tion and system design: the use of a look-alike zeotropic
mixture such as R407C; the use of higher pressure,
nearly-azeotropic mixtures R410A or R410B; and the
use of the lower pressure refrigerant HFC134a 7. By
examining these alternatives, all the major issues related
to CFC and HCFC substitution emerge and will be
briefly discussed.
Look-alike zeotropic alternatives
The special features of zeotropic mixtures present both
drawbacks and possible advantages when used in
refrigeration technology in place of a single-component
refrigerant. Specially tailored zeotropic blends used in
heat pumps with distillation, partial condensation
devices and rectifiers may offer an effective means of
obtaining capacity modulation, by suitably changing
489
HFC-32
4.5/21,5/74
Figure
HFC-23 HFC-134a
4 Vapourleakage path for a mixture of HFC-23/32/134a
Figure 4 Evolution en cas defuites de vapeurpour un m~lange de HFC-
23/32/134a
the circulation-mixed refrigerant composition. The
development of these techniques is still at an early stage
of research and will not be treated in any further
detail here 8.
However, some major concerns in the use of zeotropic
mixtures are just consequences of fractionation, which
derives from the difference in composition between
liquid- and vapour-phase at thermodynamic equili-
brium. Fractionation may cause a change in overall
composition of the residual mixture as a consequence of
leakage from a component of the refrigerating circuit
where the refrigerant is present in both phases. It is
evidently desirable that the equipment be topped up after
a leakage with the as-formulated composition refriger-
ant, without suffering noticeable adverse changes in
performance, and without the composition shifting to
the flammable region if, as is the case with R407C, the
non-flammable mixed refrigerant contains a flammable
component. This occurs in most situations with the
proposed mixtures, as experimenting and simulation
results indicate. Only in extreme cases would servicing a
system after a fluid loss require the removal of the residual
refrigerant and its replacement with a new charge.
The possibility of formulating mixtures with one flam-
mable component and still obtaining a non-flammable
refrigerant is being widely exploited in creating chlorine-
free mixed alternatives to R502 and HCFC22, as is shown
in Table 2. Either HFC32 or HFCI43a are present in all
the halogenated mixtures listed in Table 2; both these fluids
are moderately flammable (ASHRAE rating A2), but with
desirable thermodynamic properties from which blends
may benefit9.
The change in composition during fractionation of
zeotropic mixtures has to be duly taken into account in
the formulation of a safe blend in terms of flammability,
and in fact ASHRAE Standard 34-1992 on number
designation and safety classification of refrigerants
requires zeotropic blends (containing a flammable and/
or a toxic component) to be assigned a dual safety group
classification, the first for the as-formulated composition
of the blend, and the second for the worst case of
fractionation.
Figure 3 shows the vapour flammability boundaries (at
ambient pressure, and temperatures 25 and 100°C) of
490 A. Cavallini

Table 2 Chlorine-free alternative refrigerants

Tableau 2 L'rigorig~ne de remplacement sans chlore

ASHRAE no. Composition NBP* (°C) GWP* Brand

(rating) (% mass f.) (bubble/glide) (CO2 = 1) Replacing name

R23 -82.1 12100 * C F C I 3/BFC/13B1

*R503/mix. comp.
R32 -51.7 580 mixture component
(A2)
R 125 -48.6 3200 mixture component
(Al)
R134a -26.1 1300 *CFCI2/HCFC22
(A 1) mixture component
R 143a -47.4 4400 mixture component
(A2)
R 152a -24.7 150 mixture component
(A2)
R218/134a/600a ( - 35,0/5.2) 1800~t * C F C 12 IsceonTM 49 (RX2)
(9/88/3) >4200 §
R404A R 125/143a/134a (-46.5/0.8) 3700 * R502/HCFC22 Forane TM FX70
(A1/A1) (44/52/4) Meforex TM M55
ReclinTM 404A
SuvaTM HP 62
R407A R32/125/134a (-45.5/6.6) 1900 * R502 Klea TM 407A
(A 1/A 1) (20/40/40)
R407B R32/125/134a (-47.3/4.4) 2600 CFC 12/*R502 Klea TM 407B
(A1/AI) (10/70/20)
R407C R32/125/134a (-44.0/7.2) 1600 *HCFC22 Genetron TM 407C
(A1/A1) (23/25/52) Klea TM 407C
MeforexTM M95
ReclinTM HX3
SuvaTM 9000
R32/125/143a (-49.7/0.9) 3500 * R502 Forane TM FX 40
(10/45/45)
R410A R32/125 (-52.7/<0.1) 1900 HCFC22 Genetron TM AZ 20
(A1/A1) (50/50) Solkane TM 410A
R410B R32/125 (-51.8/<0.1) 2000 HCFC22 SuvaTM 9100
(A1/A1) (45/55)
R32/125/143a/134a (-49.4/4.1) 3000 HCFC22/*R502 ReclinTM HX4
(10/33/36/21)
R23/32/134a (-43.0/10.2) 1600 *HCFC22 Forane TM FX 220
(4.5/21.5/74)
R507 R125/143a -46.7 (azeo) 3800 R502 Genetron TM AZ 50
(Al) (50/50) Meforex TM M57
R125/290/218 -54.6 (nearm) *BFC13BI IsceonTM 89 (RX4)
(R508) Ir R23/116 -85.7 (azeo) 12300 * C F C I 3/*R503 Klea TM 508
(A1) II (39/61)
R23/116 - 8 8 (nearm) 12300 *CFC13/*R503 Suva TM 95
(46/54)
R32/134a (-40.4/7.2) 1100 *HCFC22
(25/75)
R290/600 (-31.6/12.3) 3 *CFC12 OZI2
(50/50)
R717 -33.3 neglig. HCFC22/R502
(B2)
* Boiling point or (bubble point/temperature glide) at p = 1 atm. Temperature glide: (Tdcw - Tbubb~e)
t l T H = 100 years
~;According to ref. 28, where GWPI00 = 7000 is attributed to FC218
§According to ref. 29, where GWP10o > 34000 is attributed to FC218
IIAssignment pending
* Look-alike alternative
(Some ASHRAE designations or ratings are still under public review)

ternary mixtures of HFC32, HFC125 and HFC134a.
The nominal compositions of several blends considered
as alternatives to R502 and HCFC22 are indicated
(symbol *, marked L). Further, the diagram shows the
composition of the charge in a system mistakenly
vapour-charged from a large canister, where the liquid
is at the nominal composition L (points marked V/L).
Finally, a third point V is reported for any blend,
corresponding to the first vapour composition which
could leak from the system, where the charge had been
 Working fluids for mechanical refrigeration
T capacity component when flooded evaporators are
b geq
T c = Ta2
Tc
Ta~
J
Tot.
T, t
_1
m nop
Figure 5 Comparison between idealized Carnot and Lorenz reverse
cycles
Figure 5 Comparaison entre les cycles id~aux inverses de Carnot et de
Lorenz
liquefied; data in Figure 3 are calculated with reference to
equilibrium compositions at +10°C.
Checking that this two-step fractionation path keeps
within the non-flammable region is a rather conservative
criterion to rate a blend as to flammability; it is not part
of an official test procedure, though it has been used by
some refrigerant manufacturers 2.
Figure 3 evidences the substantial improvement in
safety displayed by the present formulation of R407C
blend, as compared to the previous composition (30/10/
60% mass fraction) that two major refrigerant manu-
facturers were at first considering.
Figure 4 shows the composition path referring to a low
temperature (-33°C), slow vapour leak for the zeotropic
blend HFC23/32/134a (4.5/21.5/74) proposed as a look-
alike substitute for HCFC22 in air-conditioning appli-
cations. The situation depicted has been identified as
corresponding to the worst case of fractionationl°. Details
of requirements for fractionation analyses in relation to
flammability of refrigerant blends are specified in
ASHRAE Standard 34, 1992 (section 8, currently under
public review), and in UL Standard 2182, 1995.
Fractionation of zeotropic refrigerant mixtures strictly
requires that system charging and refilling be made with
liquid-phase refrigerant from the bottom of a charging
cylinder, to make sure that the composition of the fluid
entering the system is practically the nominal composi-
tion of the blend.
Modelling and computer simulations of leakage and
charging processes with zeotropic refrigerant mixtures
are very useful tools for rapid analysis of fractionation
scenarios; an excellent methodology for leakage analyses
is reported in ref. 11.
Fractionation may cause problems not only in
connection with leakages or charging of a circuit. Early
tests of zeotropic mixtures in packaged multi-split
equipment, with a few indoor units fed by a single
outdoor unit showed erratic system operation due to
composition shift when one of the indoor evaporators
was not working. Furthermore, as a result of fractiona-
tion, the composition of the circulating refrigerant may
491
be considerably richer in the more volatile, higher-
employed, such as in large water chillers with screw or
centrifugal compressors; a zeotropic refrigerant blend
with a significant glide like R407C is not therefore
considered suitable for use in these systems, although
some applications have been attempted. It is worthwhile
noting that a composition shift in the circulating
refrigerant can also be caused (in both zeotropic and
azeotropic blends) by differential solubility of the
mixture components in the lubricant.
The existence of temperature glides during constant
pressure condensation and evaporation processes is a
feature connected with fractionation of zeotropic mix-
tures which, depending on the circumstances, can benefit
or penalise system operation. In air-source heat pumps,
because of the temperature glide exhibited by R407C,
frost is formed on the outside heat exchanger at higher
outdoor temperature than with R22. On the other hand,
in direct expansion air conditioners, the existence of a
temperature glide improves dehumidification of pro-
cessed air.
It may be difficult to deal with temperature glide in a
reversible heat pump. In water-source heat pumps, the
water exchanger is usually piped in parallel flow during
the heating mode, and freeze-up problems may arise as a
result of the low temperature of the refrigerant entering
the exchanger ~2. To overcome this problem, it may
sometimes be necessary to select a heat exchanger with
significant refrigerant-side pressure drop in order to
decrease the temperature glide. In fact, a pressure drop
affects glide: it reduces the glide in a direct expansion
evaporator, whereas it increases the temperature glide in
flow condensers.
When considering zeotropic mixtures, this unique
characteristic of variable temperature phase change
under constant pressure offers a potential improvement
of the refrigeration efficiency by closely matching the
refrigerant temperature profile with the sink and/or
source fluid's temperature profile. As an ideal reference
for the vapour compression refrigeration process with a
zeotropic mixture a Lorenz cycle can be assumed in place
of a reverse Carnot cycle 13'14. The ideal Lorenz cycle
considers two constant-heat capacity processes during
which heat transfer takes place, and two constant-
entropy adiabatic processes involving compression and
expansion.
To gain a first-approximation assessment of the
potential of this temperature-matching issue, one can
Lrst refer to the fully idealized situation depicted in the
diagram (T is absolute temperature, S is entropy rate) in
Figure 5, where the situation examined considers
constant specific heat for external fluids through pre-
determined temperature transitions: (T01 -~ T02) for the
fluid cooled in the evaporator; (T~1 ~ Ta2 ) for the
condenser cooling fluid.
With single-component refrigerants (or azeotropic
mixtures), the reverse Carnot cycle is the ideal reference
for the refrigeration process; the Carnot cycle (bcdeb) in
Figure 5 operating between temperatures Tc = Ta2 at the
condenser and Te = T02 at the evaporator represents
the limit for compatibility under the temperature
constraints of the external fluids. The corresponding
evolutions of the external fluids are f ~ q at the high-
temperature exchanger (condenser), and h ~ c at the low-
492 A. Cavallini
0.7 dml
ds
0
0.1
O.I
C densation temperature (At~ = T ~ - irc) and in the
O.q
0 0.2 0 . 4 0 . 6 0 . 8 1 1.2 1.4 1.61.8 2
d
Figure 6 Diagram to compute the temperature gain values At* in the
reference temperatures of refrigerant in a reverse Lorenz cycle, as
compared to those in a Carnot reverse cycle. Atml is the countercurrent
logarithmic mean temperature difference; the other symbols are defined
in the diagram
Figure 6 Diagramme pour l'estimation des valeurs du gain de
temperature At* pour les temperatures de r~fdrence du frigorigkne clans
un cycle de Lorenz inverse, par comparaison avec celles du cycle de
Carnot inversd. A t m l est la diffdrence des tempdratures en moyenne
logarithmique g~contre-courant; les autres symboles sont ddfinis clans la
diagramme
temperature exchanger (evaporator), with area(fqpmf) =
area(ebmoe) and area(hcmnh) = area(dcmod).
Although the two heat exchangers have zero effective
mean temperature differences (and would therefore
require heat transmittance-~ oc), they are sources of
unavoidable thermodynamic irreversibility due to the
temperature mismatch between the refrigerant and the
external fluid during heat transfer, which takes place
over finite temperature differences. Area(stons) and
area(otupo) in Figure 5 represent the exergy loss rates
at the evaporator and the condenser respectively, with
Tal being the natural choice for the reference ambient
temperature in this circumstance.
Working with a zeotropic mixed refrigerant makes it
conceptually possible to eliminate any thermodynamic
irreversibility by perfectly matching the refrigerant
temperature profiles in counter-flow heat exchangers
through execution of the ideal reverse Lorenz cycle
(hgfch), performing the same cooling duty as the
previously considered reverse Carnot cycle. In this case,
the evolutions of the external fluids are h ~ c and f ~ g,
respectively, for the evaporator and the condenser.
The area enclosed by a (reversible) cycle in the diagram
in Figure 5 represents the required power input. Thus,
the difference in area between the two cycles yielding
the same refrigeration duty emphasises the superior
energy efficiency of the Lorenz cycle as compared to the
Carnot cycle.
To calculate the increase in COP obtained by referring
to the Lorenze cycle rather than to the Carnot cycle, one
must consider that the ideal COP of the Lorenz cycle
can be computed by the usual Carnot expression:
C O P = _ Te
Tc-~o
where irc and Te are the mean thermodynamic tempera-
tures of the refrigerant in the evaporator and the
condenser, respectively (ratio of the enthalpy variation
over the entropy variation). Moreover, in typical
conditions of normal refrigeration and heat pump
operations, no appreciable error is made by approxi-
mating the mean thermodynamic temperatures with the
mean arithmetic temperatures of the refrigerant heat-
transfer processes.
One can then compute the improvement in COP by
considering the Carnot expression in relation to the
temperature gains At* both in the reference con-
reference evaporation temperature (At~ = ire -T~),
obtainable by referring to the Lorenz cycle instead of
the Carnot cycle.
As shown in Figure 5, the temperature gains At* are
equal to half the external fluid temperature transitions
for the fully idealized situation examined above:
At~hd = (Ta2 - Tal)/2, Ate]id = (Tin - T02)/2
The ideal limit assumptions of zero temperature
approach and perfectly matched flow heat capacities of
the streams in the heat exchangers can be relaxed by
considering finite temperature approaches Am in the
exchangers with change of refrigerant phase at constant
temperature, and flow heat capacity mismatch para-
meters R for the exchangers with change of refrigerant
phase at gliding temperature:
R = Ar/Ae
where
Ar = temperature range of the refrigerant
Ae = temperature range of the external fluid.
The temperature gain values At* both at the evapora-
tor and the condenser can then be calculated, under the
constraint of equal values for the counter-current log-
mean temperature differences in the corresponding
exchangers of the Carnot and Lorenz ideal refrigeration
cycles.
Figure 6 shows the results of this computation,
expressed in terms of non-dimensional parameters. The
temperature profiles shown in Figure 6 refer to the high-
temperature exchanger, but the diagram can be applied
to the evaporator as well, with reference to appropriate
equivalent parameters.
Once the temperature gains Ate and Ate, and thus
also the reference temperatures T~ and ir~ have been
computed, the relative COP improvement can be
calculated by applying the relationship:
A(COP)_ 1 At;+ Tc .'~
cop rc - L Ate)
which clearly shows the role of the glide-to-lift ratios in
determining the effectiveness of the Lorenz concept.
 Working fluids for mechanical refrigeration
The analytical correlation among the parameters
defined in Figure 5 is:
as = 5 - - (1 - R) d for R :fi 1
+ 1) -1
and
ds=-~-
I In
1
1) dI for R = 1
As an example, in heat exchangers with a temperature
range Ae = 10°C and a pinch point Am = 5°C (repre-
sentative design parameters of an air-cooled condenser),
the maximum (R = 1) temperature gain is
At* = ds Ae = 0.09 x 10 = 0.9°C. For a reversible
cycle taking place between 0 and 40°C, this temperature
gain brings about a COP improvement of 2.25%
(condenser) and 2.58% (evaporator), giving a total
improvement of 4.83%. This improvement lessens as
the temperature lift of the cycle increases.
Observing that in most applications fractionation may
limit the maximum acceptable temperature glide of a
zeotropic refrigerant to 7-10°C, the diagram in Figure 5,
although referring to theoretical processes, indicates that
in common situations one should not expect much in
terms of energy efficiency improvement if advantage is
taken of the temperature glides with a zeotropic
refrigerant such as R407C in the heat exchangers.
Furthermore, it must be noted that, while in some
systems with water- (or brine)-to-refrigerant heat
exchangers it may be relatively straightforward to
resort to counter-flow arrangements, with air-to-
refrigerant heat exchangers only 'quasi-counterflow'
arrangements with special design are practicable.
It can be concluded that only with large temperature
ranges of external fluids (i.e. 20°C or more), reduced
cycle temperature lifts and close approach temperature
in the heat exchangers can substantial improvements in
energy efficiency be pursued by matching the gliding
temperature profiles during change of phase of suitably
tailored zeotropic mixtures.
In principle other potential performance benefits are
possible by exploiting zeotropic glides, for example by
using two-phase liquid line/suction line heat exchan-
gers or combined subcooler/evaporator unit in the
refrigerating circuit15; these possibilities, which require
substantial hardware design changes, are not dealt
with here.
When working with zeotropic mixtures, generally a
further penalty has to be paid in terms of heat-transfer
degradation, during both the condensation and evapora-
tion processes 16. In condensation heat transfer, the
added mass-transfer resistance in the vapour phase
caused by accumulation of the more volatile compound
at the vapour-liquid interface is responsible for the
lower coefficients measured as compared to pure fluids,
with shell-side condensation being particularly penalised
by this occurrence.
In boiling heat transfer with zeotropic mixtures, loss of
wall superheat and mass-transfer resistance are respon-
sible for a degradation in heat-transfer rates, as
493
compared to pure components under equivalent working
conditions.
Moreover, as refrigerants are mixed, liquid thermal
conductivity decreases and liquid viscosity increases
more than predicted by a simple linear interpolation of
the component properties, and this penalises heat
transfer, both in film condensation and in flow
evaporation.
Generally speaking, it can be assumed that the value of
the change-of-phase temperature glide of a zeotropic
mixture gives an indication of the potential heat-transfer
degradation in phase-change processes in comparison
with the mass-fraction linearly interpolated values of
pure components.
The above discussion, of course, does not necessarily
imply that the heat-transfer coefficient of a zeotropic
mixture serving as a replacement refrigerant is always
smaller than that of the original fluid.
Enhanced heat transfer with change of phase of
zeotropic mixtures is still wide open to basic and applied
research; some preliminary experimentation is being
carried out in research laboratories and some first results
are starting to appear in open literature.
High- and low-pressure alternatives
In the preceding paragraph, a few concerns about the use
of zeotropic mixtures as substitute refrigerants, and
namely of R407C as an alternative to HCFC22, have
been discussed in some detail. Only by gaining complete
field experience will some presently open points, which
cannot be overlooked, receive clear answers.
Whenever possible, choosing a look-alike alternative
as substitute refrigerant is certainly the most attractive
option, as it calls for minor modifications and adapta-
tions to currently operating equipment, therefore making
R407C the most likely replacement for HCFC22 in the
interim in most applications, except when fractionation
may be the cause of concern.
Alongside R407C, another two alternatives are being
considered for replacing HCFC22, both of them free
from concerns .about zeotropic behaviour: the higher
pressure nearly azeotropic blends of the R410 family,
and the lower pressure fluid HFC134a. However, both
these options require complete system redesign for
optimum operation.
R410A has about 50% higher saturation pressure vs
temperature as compared to HCFC22, and this deeply
affects the characteristics of system components. Com-
pressors, especially for air-cooled systems, may need
complete redesign with stronger pressure-containing
structures to pass standard tests, higher bearing loads
and larger motors (compressors of the same displaced
volume are compared). The lower vapour volume
flowrate for a given cooling capacity requires optimisa-
tion of heat exchangers, with smaller diameter tubing
and possibly different circuiting.
It is believed that a fully optimised system for use of
R410 could display a better energy efficiency as
compared to its HCFC22 counterpart, as a result of
the more favourable pressure level, which lends itself to
improved compressor efficiency and reduced energy
losses in other system components, even contrary to
simple thermodynamic cycle analyses that indicate a
slightly better efficiency for HCFC22. This efficiency
494 A. Cavallini
advantage could balance the cost of redesign and
retooling, and could permit compliance to new higher
efficiency standards that may be implemented for unitary
systems in the future.
R410 blends are gaining favourable support as the
most likely HCFC22 long-term alternative for general
air-conditioning applications, except with centrifugal
chillers, for which HFC134a appears to be a more
attractive choice.
HFC134a, which is a look-alike alternative for
CFC12, requires a volumetric compressor displacement
about 50% greater than that of a HCFC22 compressor
of the same cooling capacity, due to lower pressure vs
temperature correlation at saturation. For the same
reason, on the basis of the same cooling capacity, a
HFC134a system needs larger tubing than its
HCFC22 counterpart to keep energy losses within
appropriate limits. As a consequence, the system
would need to be physically larger and more expensive
to manufacture.
HFC 134a is therefore considered a possible long-term
substitute for HCFC22 only in centrifugal or large screw
compressor chillers, for which shell-side evaporation and
condensation make the zeotropic R407C blend unsui-
table, and where the higher speed (for centrifugal
compressors) and strengthened shell structures needed
for R410 set this alternative aside.
An additional alternative for those same systems could
be the R404A blend, a very low-glide mixture with
properties close to those of HCFC22, and therefore
requiring minor redesign. This mixture is now being
investigated as a possible replacement for R502. How-
ever, one possible drawback is its high GWP index value,
but, of course, TEWI value should be given higher
priority. As with all mixtures containing HFC125, a loss
of efficiency may be experienced at high condensation
temperatures, due to the low critical temperature of this
mixture component.
Natural fluids
A fully environment-friendly option, at least with regard
to the direct effect of the refrigerant, can be achieved only
by resorting to natural fluids, that is, substances that are
part of the global ecological system, and therefore have
no yet unknown harmful side effects. Among the various
possible natural fluids, certain hydrocarbons (HC),
ammonia, carbon dioxide, water and air are applicable
as refrigerants.
Besides their friendliness to the global environment,
natural fluids possess other positive properties, such as
their low cost, abundant availability not subject to
monopoly, no recycling is required except for local
requirements (e.g. flammable fluids), favourable thermo-
dynamic and transfer properties (most HCs considered
as replacement refrigerants, ammonia, and partly CO2)
and lower molecular mass than that of synthesised
refrigerants, which leaves room for improved compres-
sor design. Unfavourable aspects of natural fluids mainly
concern local and environmental safety, such as in the
use of the highly flammable HCs and the moderately
flammable and toxic NH3; the high process pressure and
low critical temperature of CO2; the extremely low
process pressure with water; and the low energy efficiency
of air cycles of the present generation.
The introduction of natural refrigerants in new sectors
of refrigeration requires thorough research in the
development of improved technology in processes and
components suitably adapted to their positive and
negative properties, and the formulation of safety
codes of practice and standards for system and
component design, installation and operation 17.
In particular, for ammonia and hydrocarbon applica-
tions there is a great need for uniform international
regulations and standards based on accepted quantita-
tive risk assessment studies; this, however, seems a
distant possibility although this effort is currently under
way within the EU 18'19.
Equipment working with natural refrigerants will no
doubt be favoured in the future by an expected market
awareness towards environmental protection.
The International Institute of Refrigeration is dedicat-
ing particular attention to innovative applications for
natural refrigerants. An international conference on New
Applications of Natural Working Fluids in Refrigeration
and Air Conditioning took place in Hannover, Germany
in May 1994. A meeting of the I.I.R. Sections B and E
with almost the same title will be held in Aarhus,
Denmark, in September 1996, and another meeting on a
related theme will probably take place the following year
in Norway. A brief outline of the present situation on
this subject is reported in the following2°-z7.
Hydrocarbons
Due to their high flammability, the use of hydrocarbons
in new sectors is confined to simple, hermetically sealed
systems with a limited charge operating at non sub-
atmospheric pressures. The use of hydrocarbons in
domestic applicances, both as refrigerants (R600a or
R600a/R290 mixture) and as blowing agent for insulat-
ing foam (cyclopentane) is gaining wide acceptance in
Germany and other European countries. In these
applications, the charge of hydrocarbon is limited to
approximately 50 g. In single-temperature and three-star
refrigerators the energy consumption compares favour-
ably with appliances using HFC 134a.
In some northern European countries some leading
manufacturers of residential heat pumps are offering
small- to medium-sized units with propane or iso-butane
used as working fluids. It is believed that safety
implications are fully covered by simple technical
measures.
In the commercial sector, some systems are being
converted to indirect ones which enables use of hydro-
carbons (or ammonia) in the remote machine-room
under appropriate safety conditions. Another possibility
currently under investigation involves use of indirect
ammonia systems with normal brines directly supplied to
the medium-temperature cabinets, while the low-tem-
perature cabinets work with individual propane systems
whose condensers are cooled by the brine circuit.
In certain countries such as the USA, the attitude
towards flammable refrigerants is exactly the opposite, in
fact they are not pursued due to potential liability
exposure.
Ammonia
The extension of the practices for safe use of ammonia to
 Working fluids for mechanical refrigeration
new sectors in refrigeration may benefit from the
considerable practical experience gained in using this
fluid since mechanical refrigeration was introduced, in
compliance with existing codes and design standards.
Moreover, recent important steps have been made
towards an extended use of ammonia:
• The introduction of synthetic oils (PAG) that are
soluble in ammonia, making this fluid compatible
with dry expansion operation in small units, and
favouring introduction of simple solutions to the
problem of automatic oil return to the compressor.
Due to the very low liquid/gas volume ratio for
ammonia, problems may be experienced for correct
distribution and wetting of the heat transfer surface
in dry evaporators;
• The availability of canned motor-type compressors
which through extensive use of aluminium makes it
possible to achieve fully hermetic circuits;
• The construction of ammonia-compatible, soldered
plate heat exchangers which helps reduce the amount
of charged refrigerant considerably, thus satisfying a
very important safety requirement with all flammable
refrigerants.
Further developments are necessary on semi-hermetic
compatible compressors, direct-expansion plate-type
evaporators and non-welded steel and aluminium pipe
connections.
Recent new applications of ammonia involve small
direct-expansion systems for supermarket refrigeration,
water chillers and heat pumps for air conditioning of
residential buildings; all of them are, of course, closed
indirect systems. Safety precautions in the machine-room
involve closing each machine or groups of them in
suitably ventilated compartments; discharging ammonia
safely outside or through a special absorber system in
the event of leakages. Ammonia is also used exten-
sively as a working fluid in large heat pump plants for
district heating in the Nordic countries of Europe.
Central cooling, thermal storage and precooling of
combustion air of gas-turbine cogeneration plants are
other sectors where ammonia is being more and more
extensively used.
Carbon dioxide
This non-toxic and incombustible environment-
friendly refrigerant is fully compatible with normal
lubricants and common construction materials. It has a
low critical temperature (31°C), while the critical
pressure is a little below 74 bar. In normal refrigeration
applications therefore, the high-pressure heat-release
process in most cases does not involve condensation
of the refrigerant, but wide glide temperature cooling
at trans-criticat pressure, which has to be taken into
account (for example, as discussed previously with
relation to zeotropic mixtures) for energy-efficient
operations.
The coordinates of the critical point also indicate that,
when working with CO2, the pressure levels are far
higher than in conventional systems. This requires the
development of suitable components. While the high-
pressure level is usually regarded as a drawback, it does
have some positive features, such as small component
49,5
dimensions and low compression ratios which improve
compressor efficiency2°'21•
Carbon dioxide has been successfully used in a
prototype automotive air conditioner (an application
with high relative direct global warming impact when
using HFC134a), and excellent prospects are also
predicted in commercial refrigerating units with asso-
ciated tap-water heating, and in high-temperature-range
heat pumps.
Another interesting application is the use of CO2 as a
secondary refrigerant with change of phase (for example,
in low-temperature commercial applications), remotely
condensed in a refrigerating system using ammonia or
HC290 under appropriate safety conditions.
Water
Water has certain unfavourable features when used
directly as a refrigerant, that is:
• pressure levels are very low, and conversely the
specific volume of the vapour phase at low tempera-
ture is very high (180m3kg -~ at 2°C saturation
temperature), which produces a volumetric refriger-
ating capacity of approximately 0.5-1% of that of
conventional refrigerants;
• pressure ratios at normal temperature lifts are rather
high (i.e. from 5 to 7);
• when used with mechanical positive displacement
compressors, enormous swept volumes are necessary:
only turbo or specially designed rotary machines
(such as cycloid type compressors) are suitable.
On the other hand, water vapour compression plants
may be constructed as open systems, with direct-contact
heat transfer both at the evaporator and the condenser,
thus eliminating the exergy losses due to the driving
temperature differences at the surface exchangers of
traditional installations; systems with very high energy
efficiency are obtained, thus possibly making these
installations cost-competitive with traditional ones, and
for which the higher cost of the compressor can be
compensated by the energy saved during the operative
life cycle of the plant.
Mechanical compressors for water vapour refrigerat-
ing systems are commercially available today for
industrial applications in the capacity range from 500
to 5000 kW, with pressure ratios from 3 to 10 in single-
and multi-stage arrangements. Several of these plants
have recently been built and perform satisfactorily.
Another application for water, which is gaining an
increasing interest, is its use as a secondary refrigerant of
high energy density, in the form of a pumpable
suspension of microscopic ice-crystals (water-ice
slurry); this can be obtained directly in the evaporator
of a water-vapour refrigeration plant.
Air
Energy improvements in standard air-cycle machines are
necessary if they are to be made competitive with
conventional systems in the normal refrigeration tem-
perature range. These improvements can be achieved
with high-performance components (compressors,
expanders, heat exchangers) and modifications to the
496 A. Caval/ini
basic configurations which include open systems, regen-
erative heat exchangers, multi-stage compression and
expansion and intelligent use of humidity in the
processed air. Promising innovative applications are:
systems for very-low temperature uses, refrigerated
transport of foodstuffs, food chilling, plants with both
heating and cooling loads, and perhaps automotive and
railway-car air conditioning.
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