CHAPTER 7

LUBRICANTS IN REFRIGERANT SYSTEMS

Tests for Boundary Lubrication ................................................ 7.1 Wax Separation (Floc Tests) ................................................... 7.18
Refrigeration Lubricant Requirements ..................................... 7.2 Solubility of Hydrocarbon Gases ............................................ 7.20
Mineral Oil Composition .......................................................... 7.2 Solubility of Water in Lubricants ............................................ 7.21
Component Characteristics ...................................................... 7.3 Solubility of Air in Lubricants ................................................. 7.21
Synthetic Lubricants ................................................................. 7.3 Foaming and Antifoam Agents ................................................ 7.21
Lubricant Additives ................................................................... 7.4 Oxidation Resistance ............................................................... 7.24
Lubricant Properties ................................................................. 7.5 Chemical Stability ................................................................... 7.25
Lubricant-Refrigerant Solutions ............................................... 7.8 Conversion from CFC Refrigerants to
Lubricant Return from Evaporators ....................................... 7.16 Other Refrigerants................................................................ 7.26

T HE primary function of a lubricant is to reduce friction and

minimize wear. A lubricant achieves this by interposing a film
between moving surfaces that reduces direct solid-to-solid contact
characteristics to reduce surface fatigue, adhesion, abrasion, and
corrosion, which are the four major sources (either singularly or
together) of rapid wear under boundary conditions. The slightly
or lowers the coefficient of friction. active constituents left in commercially refined mineral oils give
Understanding the role of a lubricant requires an analysis of them their natural film-forming properties.
the surfaces to be lubricated. Although bearing surfaces and other Additives have also been developed to improve lubrication under
machined parts may appear and feel smooth, close examination boundary conditions. These materials are characterized by terms
reveals microscopic peaks (asperities) and valleys. With a suffi- such as oiliness agents, lubricity improvers, and antiwear additives.
cient quantity of lubricant, a layer is provided that has a thickness They form a film on the metal surface through polar attraction or
greater than the maximum height of the mating asperities, so that chemical action. These films or coatings have lower coefficients of
moving parts ride on a lubricant cushion. friction under the loads imposed during boundary conditions. In
These dual conditions are not always easily attained. For exam- chemical action, the temperature increase brought about by friction-
ple, when the shaft of a horizontal journal bearing is at rest, the static generated heat brings about a reaction between the additive and the
loads squeeze out the lubricant, producing a discontinuous film with metal surface. Films such as iron sulfide and iron phosphate can be
metal-to-metal contact at the bottom of the shaft. When the shaft formed depending on the additives and the energy available for the
begins to turn, there is no layer of liquid lubricant separating the sur- reaction. In some instances, organic phosphates and phosphites are
faces. As the shaft picks up speed, the lubricating fluid is drawn into used in refrigeration oils to improve boundary lubrication. The
the converging clearance between the bearing and the shaft, gener- nature and condition of the metal surfaces are important. Refriger-
ating a hydrodynamic pressure that eventually can support the load ation compressor designers often treat ferrous pistons, shafts, and
on an uninterrupted fluid film (Fuller 1984). wrist pins with phosphating processes that impart a crystalline, dis-
Various regimes or conditions of lubrication can exist when sur- continuous film of metal phosphate to the surface. This film aids
faces are in motion with respect to one another. Regimes of lubrica- boundary lubrication during the break-in period.
tion are defined as follows:
• Full fluid film or hydrodynamic. Mating surfaces are completely TESTS FOR BOUNDARY LUBRICATION
separated by the lubricant film. Film strength or load-carrying ability are terms often used to
• Boundary. Gross surface-to-surface contact occurs because the describe lubricant lubricity characteristics under boundary condi-
bulk lubricant film is too thin to separate the mating surfaces. tions. Laboratory tests that measure the degree of scoring, welding,
• Mixed fluid film or quasi-hydrodynamic. Occasional or random or wear have been developed to evaluate lubricants. However,
surface contact occurs. bench-type tests cannot be expected to accurately simulate actual
field performance in a given compressor and are, therefore, merely
Many materials can be used to separate and lubricate contacting
screening devices. Some of these tests have been standardized by
surfaces. Separation can be maintained by a boundary layer on a
ASTM and other organizations.
metal surface, a fluid film, or a combination of both.
In the four-ball extreme-pressure method (ASTM D2783), the
The function of a lubricant extends beyond preventing surface
antiwear property is determined from the average scar diameter on
contact. It also removes heat, provides a seal to keep out contami-
the stationary balls and is stated in terms of a load-wear index. The
nants or to retain pressures, inhibits corrosion, and carries away
smaller the scar, the better the load-wear index. The maximum load-
debris created by wear. Lubricating oils are best suited to meet these
carrying capability is defined in terms of a weld point (i.e., the load
various requirements.
at which welding by frictional heat occurs).
Viscosity is the most important property to consider in choosing
a lubricant under full fluid film conditions. Under boundary condi- The Falex method (ASTM D2670) allows measurement of wear
tions, the asperities are the contact points and support much, if not during the test itself, and the scar width on the V-blocks and/or the
all, of the load; and the contact pressures are usually sufficient to mass loss of the pin can be used as a measure of the antiwear prop-
cause welding and surface deformation. However, even under these erties. The load-carrying capability is determined from a failure,
conditions, wear can be controlled effectively with nonfluid, multi- which can be caused by excess wear or extreme frictional resistance.
molecular films formed on the surface. These films must be strong The Timken method (ASTM D2782) determines the load at which
enough to resist rupturing, yet have acceptable frictional and shear rupture of the lubricant film occurs, and the Alpha LFW-1 machine
(ASTM D2714) measures frictional force and wear.
The FZG gear test facility can provide useful information on how
The preparation of this chapter is assigned to TC 3.4, Lubrication. a lubricant performs in a gear box. Specific applications include

Copyright © 2002 ASHRAE 7.1

7.2 2002 ASHRAE Refrigeration Handbook (SI)

gear-driven centrifugal compressors in which the dilution of the imparted momentum is converted into a pressure rise. Centrifugal
lubricant by a refrigerant is expected to be quite low. compressors function based on these principles.
However, because all these machines operate in air, available Refrigerant compressors require the lubricant to do more than
data may not apply to a refrigerant environment. Divers (1958) simply lubricate bearings and mechanism elements. Oil delivered to
questioned the validity of tests in air because several of the oils the mechanism serves as a barrier that separates the gas on the dis-
that performed poorly in Falex testing have been used successfully charge side from the gas on the suction sides. Oil also acts as a cool-
in refrigerant systems. Murray et al. (1956) suggest that halocar- ant, transferring heat from the bearings and mechanism elements to
bon refrigerants can aid in boundary lubrication. Refrigerant 12, the crankcase sump, which, in turn, transfers heat to the surround-
for example, when run hot in the absence of oil, reacted with steel ings. Moreover, oil helps reduce noise generated by moving parts
surfaces to form a lubricating film. These studies emphasize the inside the compressor. Generally, the higher the viscosity of the
need for laboratory testing in a simulated refrigerant environment. lubricant, the better the sealing and noise reduction capabilities.
In Huttenlocher’s (1969) method of simulation, refrigerant vapor A hermetic system, in which the motor is exposed to the lubri-
is bubbled through the lubricant reservoir before the test to displace cant, requires a lubricant with electrical insulating properties. The
the dissolved air. The refrigerant is bubbled continually during the refrigerant gas normally carries some lubricant with it as it flows
test to maintain a blanket of refrigerant on the lubricant surface. through the condenser, flow-control device, and evaporator. This
Using the Falex tester, Huttenlocher showed the beneficial effect of lubricant must return to the compressor in a reasonable time and
R-22 on the load carrying capability of the same lubricant compared must have adequate fluidity at low temperatures. The lubricant must
with air or nitrogen. Sanvordenker and Gram (1974) describe a fur- also be free of suspended matter or components such as wax that
ther modification of the Falex test using a sealed sample system. might clog the flow control device or deposit in the evaporator and
Both R-12 (a CFC) and R-22 (an HCFC) atmospheres had adversely affect heat transfer. In a hermetic system, the lubricant is
beneficial effects on a lubricant’s boundary lubrication character- charged only once, so it must function for the lifetime of the com-
istics when compared with tests in air. HFC refrigerants, which pressor. The chemical stability required of the lubricant in the pres-
are chlorine-free, provide beneficial effects to boundary lubrica- ence of refrigerants, metals, motor insulation, and extraneous
tion when compared to tests conducted in air. However, they con- contaminants is perhaps the most important characteristic distin-
tribute to increased wear as compared to a chlorinated refrigerant guishing refrigeration lubricants from those used for all other appli-
with the same lubricant. cations (see Chapter 5).
Komatsuzaki and Homma (1991) used a modified four-ball tester Although the compression components of centrifugal compres-
to determine the antiseizure and antiwear properties of R-12 and sors require no internal lubrication, rotating shaft bearings, seals,
R-22 in mineral oil and R-134a in a propylene glycol. and couplings must be adequately lubricated. Turbine or other types
Test parameters must simulate as closely as possible the system of lubricants can be used when the lubricant is not in contact or cir-
conditions (the base material from which the test specimens are culated with the refrigerant.
made, their surface condition, the processing methods, and the oper- As expected, an ideal lubricant does not exist; a compromise
ating temperature). There are several bearings or rubbing surfaces in must be made to balance the requirements. A high-viscosity lubri-
a refrigerant compressor, each of which may use different materials cant seals the gas pressure best, but may offer more frictional resis-
and may operate under different conditions. A different test may be tance. Slight foaming can reduce noise, but excessive foaming can
required for each bearing. Moreover, bearings in hermetic compres- carry too much lubricant into the cylinder and cause structural dam-
sors have very small clearances. Permissible bearing wear is mini- age. Lubricants that are most stable chemically are not necessarily
mal because wear debris remains in the system and can cause other good lubricants. The lubricant should not be considered alone,
problems even if the clearances stay within working limits. Com- because it functions as a lubricant-refrigerant mixture.
pressor system mechanics must be understood to perform and inter- The precise relationship between composition and performance
pret simulated tests. is not well defined. Standard ASTM bench tests can provide
Some aspects of compressor lubrication are not suitable for lab- such information as (1) viscosity, (2) viscosity index, (3) color,
oratory simulation. One aspect, the return of liquid refrigerant to the (4) specific gravity, (5) refractive index, (6) pour point, (7) aniline
compressor, can cause the lubricant to dilute or wash away from the point, (8) oxidation resistance, (9) dielectric breakdown voltage,
bearings, creating conditions of boundary lubrication. Tests using (10) foaming tendency in air, (11) moisture content, (12) wax sep-
operating refrigerant compressors have also been considered, and aration, and (13) volatility. Other properties, particularly those
one such wear test has been proposed as a German Standard (DIN involving interactions with a refrigerant, must be determined by
8978). The test is functional for a given compressor system and may special tests described in the refrigeration literature. Among these
permit comparison of lubricants within that class of compressors. nonstandard properties are (1) mutual solubility with various refrig-
However, it is not designed to be a generalized test for the boundary erants, (2) chemical stability in the presence of refrigerants and met-
lubricating capability of a lubricant. Other tests using radioactive als, (3) chemical effects of contaminants or additives that may be in
tracers in refrigerant systems have given useful results (Rembold the oils, (4) boundary film-forming ability, (5) solubility of air, and
and Lo 1966). (6) viscosity, vapor pressure, and density of oil-refrigerant mixtures.

REFRIGERATION LUBRICANT MINERAL OIL COMPOSITION

REQUIREMENTS For typical applications, the numerous compounds in refrigera-
Regardless of size or system application, refrigerant compressors tion oils of mineral origin can be grouped into the following struc-
are classified as either positive-displacement or dynamic (2001 ASH- tures: (1) paraffins, (2) naphthenes (cycloparaffins), (3) aromatics,
RAE Handbook—Fundamentals). The function of both types is to and (4) nonhydrocarbons. Paraffins consist of all straight chain
increase the pressure of the refrigerant vapor. Positive-displacement and branched carbon chain saturated hydrocarbons. N-Pentane
compressors increase the refrigerant pressure by reducing the vol- and isopentane are examples of paraffinic hydrocarbons. Naph-
ume of a compression chamber through work applied to the mecha- thenes are also completely saturated but consist of cyclic or ring
nism. Positive-displacement compressor mechanisms include scroll, structures; cyclopentane is a typical example. Aromatics are
reciprocating, rotary, and screw. In contrast, dynamic compressors unsaturated cyclic hydrocarbons containing one or more rings
increase the refrigerant pressure by a continuous transfer of angular characterized by alternate double bonds; benzene is a typical
momentum from the rotating member. As the gas is decelerated, the example. The nonhydrocarbons are molecules containing atoms
Lubricants in Refrigerant Systems 7.3

such as sulfur, nitrogen, or oxygen in addition to carbon and flocs in certain refrigerant solutions (see the section on Wax Sepa-
hydrogen. ration). The branched chain paraffins and naphthenes are less vis-
The preceding structural components do not necessarily exist in cous at low temperatures and have extremely low pour points.
pure states. In fact, a paraffinic chain frequently is attached to a naph- Nonhydrocarbons are mostly removed during the refining of
thenic or aromatic structure. Similarly, a naphthenic ring to which a refrigeration oils. Those that remain are expected to have little effect
paraffinic chain is attached may in turn be attached to an aromatic on the physical properties of the lubricant, except, perhaps, on its
molecule. Because of such complications, mineral oil composition color, stability, and lubricity. Because not all the nonhydrocarbons
is usually described by carbon type and molecular analysis. (e.g., sulfur compounds) are dark, even a colorless lubricant does
In carbon type analysis, the number of carbon atoms on the par- not necessarily guarantee the absence of nonhydrocarbons. Kartz-
affinic chains, naphthenic structures, and aromatic rings is deter- mark et al. (1967) and Mills and Melchoire (1967) found indications
mined and represented as a percentage of the total. Thus, % CP, the that nitrogen-bearing compounds cause or act as catalysts toward
percentage of carbon atoms having a paraffinic configuration, the deterioration of oils. The sulfur and oxygen compounds are
includes not only the free paraffins but also those paraffinic chains thought to be less reactive, with some types considered to be natural
attached to naphthenic or to aromatic rings. inhibitors and lubricity enhancers.
Similarly, % CN includes the carbon atoms on the free naphthenes Solvent refining, hydrofinishing, or acid treatment followed by
as well as those on the naphthenic rings attached to the aromatic a separation of the acid tar formed are often used to remove more
rings, and % CA represents the carbon atoms on the aromatic rings. thermally unstable aromatic and unsaturated compounds from the
Carbon analysis describes a lubricant in its fundamental structure base stock. These methods also produce refrigeration oils that are
and correlates and predicts many physical properties of the lubricant. free from carcinogenic materials sometimes found in crude oil
However, direct methods of determining carbon composition are stocks.
laborious. Therefore, common practice uses a correlative method, The properties of the components naturally are reflected in the
such as the one based on the refractive index-density-relative molec- parent oil. An oil with a very high saturate content, as is frequently
ular mass (n-d-m) (Van Nes and Weston 1951) or one standardized the case with paraffinic oils, also has a high viscosity index, low spe-
by ASTM D2140 or ASTM D3288. Other methods are ASTM cific gravity, high relative molecular mass, low refractive index, and
D2008, which uses ultraviolet absorbency and a rapid method using low volatility. In addition, it would have a high aniline point and
infrared spectrophotometry and calibration from known oils. would be less miscible with polar refrigerants. The reverse is true of
Molecular analysis is based on methods of separating the struc- naphthenic oils. Table 1 lists typical properties of several mineral-
tural molecules. For refrigeration oils, important structural mole- based refrigeration oils.
cules are (1) saturates or nonaromatics, (2) aromatics, and (3)
nonhydrocarbons. All the free paraffins and naphthenes (cyclopar- SYNTHETIC LUBRICANTS
affins), as well as mixed molecules of paraffins and naphthenes are The limited solubility of mineral oils with R-22 and R-502 orig-
included in the saturates. However, any paraffinic and naphthenic inally led to the investigation of synthetic lubricants for refrigera-
molecules attached to an aromatic ring are classified as aromatics. tion use. In more recent times, the lack of solubility of mineral oils
This representation of lubricant composition is less fundamental in nonchlorinated fluorocarbon refrigerants, such as R-134a and
than carbon analysis. However, many properties of the lubricant rel- R-32, has led to the commercial use of some synthetic lubricants.
evant to refrigeration can be explained with this analysis, and the Gunderson and Hart (1962) describe a number of commercially
chromatographic methods of analysis are fairly simple (ASTM available synthetic lubricants such as synthetic paraffins, polygly-
D2549; ASTM D2007; Mosle and Wolf 1963; Sanvordenker 1968). cols, dibasic acid esters, neopentyl esters, silicones, silicate esters,
The traditional classification of oils as paraffinic or naphthenic and fluorinated compounds. Many have properties suited to refrig-
refers to the amount of paraffinic or naphthenic molecules in the eration purposes. Sanvordenker and Larime (1972) describe the
refined lubricant. Paraffinic crudes contain a higher proportion of properties of these synthetic lubricants, alkylbenzenes, and phos-
paraffin wax, and thus have a higher viscosity index and pour point phate esters in regard to refrigeration applications using chlorinated
than to naphthenic crudes. fluorocarbon refrigerants. The phosphate esters are unsuitable for
refrigeration use because of their poor thermal stability. Although
COMPONENT CHARACTERISTICS very stable and compatible with refrigerants, the fluorocarbon lubri-
Saturates have excellent chemical stability, but poor solubility cants are expensive. Among others, only the synthetic paraffins
with polar refrigerants, such as R-22; they are also poor boundary have poor miscibility relations with R-22. Dibasic acid esters, neo-
lubricants. Aromatics are somewhat more reactive but have very pentyl esters, silicate esters, and polyglycols all have excellent vis-
good solubility with refrigerants and good boundary lubricating cosity temperature relations and remain miscible with R-22 and
properties. Nonhydrocarbons are the most reactive but are benefi- R-502 to very low temperatures. At this time, the three synthetic
cial for boundary lubrication, although the amounts needed for that lubricants seeing the greatest use are alkylbenzene, for R-22 and
purpose are small. The reactivity, solubility, and boundary lubricat- R-502 service, and polyglycols and polyol esters, for use with
ing properties of a refrigeration lubricant are affected by the relative R-134a and refrigerant blends using R-32.
amounts of these components in the lubricant. There are two basic types of alkylbenzenes: branched and linear.
The saturate and aromatic fractions separated from a lubricant do The products are synthesized by reacting an olefin or chlorinated
not have the same viscosity as the parent lubricant. The saturate paraffin with benzene in the presence of a catalyst. Catalysts com-
fraction is much less viscous, and the aromatic fraction is much monly used for this reaction are aluminum chloride and hydrofluo-
more viscous than the parent lubricant. Both fractions have the same ric acid. After the catalyst is removed, the product is distilled into
boiling range. Thus, for this range, the aromatics are more viscous fractions. The relative size of these fractions can be changed by
than the saturates. For the same viscosity, the aromatics have a adjusting the relative molecular mass of the side chain (olefin or
higher volatility than the saturates. Also, the saturate fraction has a chlorinated paraffin) and by changing other variables. The quality of
lower density and a lower refractive index, but a higher viscosity alkylbenzene refrigeration lubricant varies, depending on the type
index and molecular mass than the aromatic fraction of the same (branched or linear) and manufacturing scheme. In addition to good
lubricant. solubility with refrigerants, such as R-22 and R-502, these lubri-
Among the saturates, the straight chain paraffins are undesirable cants have better high-temperature and oxidation stability than min-
for refrigeration applications because they precipitate as wax crys- eral oil-based refrigeration oils. Typical properties for a branched
tals when the lubricant is cooled to its pour point and tend to form alkylbenzene are shown in Table 1.
7.4 2002 ASHRAE Refrigeration Handbook (SI)

Table 1 Typical Properties of Refrigerant Lubricants

Mineral Lubricants Synthetic Lubricants
Alkyl-
Property ASTM Naphthenic Paraffinic benzene Ester Glycol
Viscosity, mm2/s D 445 33.1 61.9 68.6 34.2 31.7 30 100 29.9 90
at 38°C
Viscosity index D 2270 0 0 46 95 27 111 98 210 235
Density, kg/m3 D 1298 913 917 900 862 872 995 972 990 1007
Color D 1500 0.5 1 1 0.5
Refractive index D 1747 1.5015 1.5057 1.4918 1.4752
Relative molecular mass D 2503 300 321 345 378 320 570 840 750 1200
Pour point, °C D 97 –43 –40 –37 −18 –46 –48 –30 –46 –40
Floc point, °C ASHRAE 86 –56 –51 –51 –35 –73
Flash point, °C D 92 171 182 204 202 177 234 258 204 168
Fire point, °C D 92 199 204 232 232 185
Composition Branched Branched PP monol PP diol
Carbon-type acid acid mono- di-
penta- penta- functional functional
%CA Van Nes and 14 16 7 3 24
erythritol erythritol poly- poly-
%CN Weston (1951) 43 42 46 32 None propylene propylene
%CP 43 42 47 65 76 glycol glycol
Molecular composition D 2549
% Saturates 62 59 78 87 None
% Aromatics 38 41 22 13 100
Aniline point, °C D 611 71 74 92 104 52
Critical solution temp. — −3.9 1.7 23 27 –73
with R-22, °C

Polyalkylene glycols (PAGs) derive from ethylene oxide or LUBRICANT ADDITIVES

propylene oxide. The polymerization is usually initiated either Additives are used to enhance certain lubricant properties or
with an alcohol, such as butyl alcohol, or by water. Initiation by impart new characteristics. They generally fall into three groups,
an alcohol results in a monol; initiation by water results in a diol. namely polar compounds, polymers, and compounds containing
PAGs are commonly used as lubricants in automotive air-condi- active elements such as sulfur or phosphorous. Additive types
tioning systems using R-134a. PAGs have excellent lubricity, low include (1) pour point depressants for mineral oil, (2) floc point
pour points, good low-temperature fluidity, and good compatibil- depressants for mineral oil, (3) viscosity index improvers for min-
ity with most elastomers. Major concerns are that these oils are eral oil, (4) thermal stability improvers, (5) extreme pressure and
somewhat hygroscopic, are immiscible with mineral oils, and antiwear additives, (6) rust inhibitors, (7) antifoam agents, (8) metal
require additives for good chemical and thermal stability (Short deactivators, (9) dispersants, and (10) oxidation inhibitors.
1990). Some additives offer performance advantages in one area but are
Polyalphaolefins (PAOs) are normally manufactured from lin- detrimental in another. For example, antiwear additives can reduce
ear α-olefins. The first step in manufacture is the synthesis of a the wear on compressor components, but because of the chemical
mixture of oligomers in the presence of a BF3·ROH catalyst. Sev- reactivity of these materials, the additives can reduce the overall sta-
eral parameters can be varied to control the distribution of the bility of the lubricant. Some additives work best when combined
oligomers so formed. The second step involves a hydrogenation with other additives. They must be compatible with materials in the
processing of the unsaturated oligomers in the presence of a system (including the refrigerant) and be present in the optimum
metal catalyst (Shubkin 1993). PAOs have good miscibility with concentration; too little may be ineffective, whereas too much can
R-12 and R-114. Some R-22 applications have been tried but are be detrimental or offer no incremental improvement.
limited by the low miscibility of the fluid in R-22. PAOs are In general, additive lubricants are not required to lubricate a re-
frigerant compressor. However, lubricants that contain additives
immiscible in R-134a (Short 1990). PAOs are mainly used as an
give highly satisfactory service and some additives, such as anti-
immiscible oil in ammonia systems.
wear additives, offer some performance advantages over straight
Neopentyl esters (polyol esters) are derived from a reaction mineral oils. Their use is justified as long as the user knows of
between an alcohol and a normal or branched carboxylic acid. their presence and provided the additives are not significantly de-
The most common alcohols used are pentaerythritol, trimethylol- graded with use. Additives can often be used with synthetic lubri-
propane, and neopentyl glycol. For higher viscosities, a dipen- cants to reduce wear because, unlike mineral oil, they do not
taerythritol is often used. The acids are usually selected to give contain sulfur.
the correct viscosity and fluidity at low temperatures matched to An additive lubricant is only used after thorough testing to deter-
the miscibility requirements of the refrigerant. Complex neopen- mine whether the additive material (1) is removed by system dryers,
tyl esters are derived by a sequential reaction of the polyol with a (2) is inert to system components, (3) is soluble in refrigerants at
dibasic acid followed by a reaction with mixed monoacids (Short low temperatures so as not to cause deposits in capillary tubes or
1990). This results in a lubricant with a higher relative molecular expansion valves, and (4) is stable at high temperatures to avoid
mass, high viscosity indices, and higher ISO viscosity grades. adverse chemical reactions such as harmful deposits. This can best
Polyol ester lubricants are used commercially with HFC refriger- be done by sealed tube and compressor testing using the actual addi-
ants in all types of compressors. tive/base lubricant combination intended for field use.
Lubricants in Refrigerant Systems 7.5

LUBRICANT PROPERTIES Table 2 Recommended Viscosity Ranges

Viscosity and Viscosity Grades Small and Commercial Systems

Viscosity defines a fluid’s resistance to flow. It can be expressed Lubricant Viscosities
as absolute or dynamic viscosity (mPa·s), or kinematic viscosity Type of at 38°C,
(mm2/s). In the United States, dynamic viscosity is expressed in Refrigerant Compressor mm2/s
Saybolt Seconds Universal viscosity (abbreviated SSU or SUS), Ammonia Screw 60-65
which is the time required for 60 cm3 to gravity flow through a Say-
Reciprocating 32-65
bolt universal viscometer. ASTM Standard D2161 contains tables
to convert SSU to kinematic viscosity. The density must be known Carbon dioxide Reciprocating 60-65a
to convert kinematic viscosity to absolute viscosity; that is, absolute Refrigerant 11 Centrifugal 60-65
or dynamic viscosity (mPa·s) equals density (g/cm3) times kine- Refrigerant 12 Centrifugal 60-65
matic viscosity (mm2/s). Refrigeration oils are sold in viscosity Reciprocating 32-65
grades, and ASTM has proposed a system of standardized viscosity Rotary 60-65
grades (D2422). Refrigerant 123 Centrifugal 60-65
In selecting the proper viscosity grade, the environment to which Refrigerant 22 Centrifugal 60-86
the lubricant will be exposed should be considered. The viscosity of Reciprocating 32-65
the lubricating fluid decreases if temperatures rise or if the refriger- Scroll 60-65
ant dissolves appreciably in the lubricant. Synthetic oils, with the
Screw 60-173
exception of alkyl benzenes, are less affected by temperature change
than mineral oils. Refrigerant 134a Scroll 22-68
A large reduction in the viscosity of the lubricating fluid may Screw 32-100
affect the lubricity and, more likely, the sealing function of the lubri- Centrifugal 60-65
cant, depending on the nature of the machinery. The design of some Refrigerant 407C Scroll 22-68
types of hermetically sealed units, such as the single-vane, rotary Reciprocating 32-687
units, requires the lubricating fluid to act as an efficient sealing Refrigerant 410A Scroll 22-68
agent. In reciprocating compressors, the lubricant film is spread Halogenated refrigerants Screw 32-800
over the entire area of contact between the piston and the cylinder
wall, providing a very large area to resist leakage from the high- to Industrial Refrigerationb
the low-pressure side. In a single-vane rotary type, however, the crit- Lubricant Viscosities
ical sealing area is a line contact between the vane and a roller. In Type of Compressor at 38°C, mm2/s
this case, viscosity reduction is serious.
The lubricant with the lowest viscosity that gives the necessary Where lubricant may enter refrigeration
sealing properties with the refrigerant used for the entire range of system or compressor cylinders 32-65
temperatures and pressures encountered should be chosen to mini- Where lubricant is prevented from entering
mize power consumption. A practical method for determining the system or cylinders:
minimum safe viscosity is to calculate the total volumetric efficiency In force-feed or gravity systems 108-129
of a given compressor using several lubricants of widely varying vis- In splash systems 32-34
cosities. The lubricant of lowest viscosity that gives satisfactory vol- Steam-driven compressor cylinders when High viscosity lubricant
umetric efficiency should be selected. Tests should be run at several condensate is reclaimed for ice-making (30-35 mm2/s at 100°C)
ambient temperatures, for example, 20, 30, and 40°C. As a guide- aSome applications may require lighter lubricants of 14-17 mm2/s; others, heavier
line, Table 2 lists the viscosity ranges recommended for various lubricants of 108-129 mm2/s.
bAmmonia and carbon dioxide compressors with splash, force-feed, or gravity circu-
refrigeration systems.
lating systems.
The International Organization for Standardization (ISO) has
established a series of viscosity levels as a standard for specifying or
selecting lubricant for industrial applications. This system, covered This relationship is the basis for the viscosity-temperature charts
in the United States by ASTM D2422, is designed to eliminate inter- published by ASTM and permits a straight line plot of viscosity over
mediate or unnecessary viscosity grades while providing enough a wide temperature range. Figure 1 shows a plot for two different
viscosity grades for operating equipment. The system reference lubricants, such as a naphthenic mineral oil (LVI) and a synthetic
point is kinematic viscosity at 40°C, and each viscosity grade with lubricant (HVI). This plot is applicable over the temperature range
suitable tolerances is identified by the kinematic viscosity at this in which the oils are homogenous liquids.
temperature. Therefore an ISO VG 32 grade lubricant would iden- The slope of the viscosity-temperature lines is different for differ-
tify a lubricant with a viscosity of 32 mm2/s at 40°C. Table 3 lists ent lubricants. The viscosity-temperature relationship of a lubricant
various standardized viscosity grades of lubricants. is described by an empirical number called the viscosity index (VI)
(ASTM D2270). A lubricant with a high viscosity index (HVI) shows
Viscosity Index less change in viscosity over a given temperature range than a lubri-
Lubricant viscosity decreases as temperature increases and cant with a low viscosity index (LVI). In the example shown in Figure
increases as temperature decreases. The relationship between tem- 1, both oils possess equal viscosities (32 mm2/s) at 40°C. However,
perature and kinematic viscosity is represented by the following the viscosity of the LVI lubricant (a naphthenic mineral oil), as shown
equation (ASTM D341): by the steeper slope of the line, increases to 520 mm2/s at 0°C,
whereas the HVI lubricant (a synthetic lubricant) viscosity increases
log log ( ν H 0.7 ) Z A H B log T (1) only to 280 mm2/s.
The viscosity index is related to the composition of the mineral
where oil. Generally, an increase in cyclic structure, aromatic and naph-
ν = kinematic viscosity, mm2/s, 2 ≤ ν ≤ 2 × 107 thenic, decreases the viscosity index. Paraffinic oils usually have a
T = thermodynamic temperature, K high viscosity index and low aromatic content. Naphthenic oils, on
A, B = constants for each lubricant the other hand, have a lower viscosity index and are usually higher
7.6 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 1 Viscosity-Temperature Chart for 108 HVI and LVI Fig. 2 Variation of Refrigeration Lubricant Density
Lubricants with Temperature

Fig. 1 Viscosity-Temperature Chart for 108 HVI and LVI

Lubricants

Table 3 Viscosity System for Industrial Fluid Lubricants

(ASTM D 2422)

Viscosity Kinematic Viscosity Limits,

Midpoint
System Grade mm2/s at 40°C
Viscosity,
Identification mm2/s at 40°C Minimum Maximum
ISO VG 2 2.2 1.98 2.42
ISO VG 3 3.2 2.88 3.52
ISO VG 5 4.6 4.14 5.06
ISO VG 7 6.8 6.12 7.48 Viscosity at
Lubricant 38°C, mm2/s Ref.
ISO VG 10 10 9.00 11.00
A Naphthene 64.7 1
ISO VG 15 15 13.50 16.50 B Naphthene 15.7 1
ISO VG 22 22 19.80 24.20 C Paraffin 64.7 1
ISO VG 32 32 28.80 35.20 D Paraffin 32.0 1
E Branched acid POE 32 2
ISO VG 46 46 41.40 50.60 F Branched acid POE 100 2
ISO VG 68 68 61.20 74.80 G Polypropylene glycol mono butyl ether 32 2
ISO VG 100 100 90 110 H Polyoxypropylene diol 80 2
ISO VG 150 150 135 165 References: 1. Albright and Lawyer (1959) 2. Cavestri (1993)

ISO VG 220 220 198 242

ISO VG 320 320 288 352 Fig. 2 Variation of Refrigeration Lubricant Density
ISO VG 460 460 414 506 with Temperature
ISO VG 680 680 612 748 Density indicates the composition of a lubricant for a given vis-
ISO VG 1000 1000 900 1100 cosity. As shown in Figure 2, naphthenic oils are usually more dense
ISO VG 1500 1500 1350 1650 than paraffinic oils and synthetic lubricants are generally more
dense than mineral oils. Also, the higher the aromatic content, the
higher the density. For equivalent compositions, higher viscosity
in aromatics. For the same base lubricant, the viscosity index de- oils have higher densities, but the change in density with aromatic
creases with increasing aromatic content. Generally, among com- content is greater than it is with viscosity.
mon synthetic lubricants, polyalphaolefins, polyalkylene glycols,
and polyol esters will have high viscosity indices. As shown in Relative Molecular Mass
Table 1, alkylbenzenes have lower viscosity indices.
In refrigeration applications, the relative molecular mass of a
lubricant is often needed. Albright and Lawyer (1959) showed that,
Density on a molar basis, Refrigerants 22, 115, 13, and 13B1 have about the
Figure 2 shows published values for pure lubricant densities over same viscosity-reducing effects on a paraffinic lubricant.
a range of temperatures. These density-temperature curves all have For most mineral oils, a reasonable estimate of the average molec-
approximately the same slope and appear merely to be displaced ular mass can be obtained by a standard test (ASTM D2502), based
from one another. If the density of a particular lubricant is known at on kinematic viscosities at 40°C and 100°C; or from viscosity-
one temperature but not over a range of temperatures, a reasonable gravity correlations of Mills et al. (1946). Direct methods (ASTM
estimate at other temperatures can be obtained by drawing a line D2503) can also be used when greater precision is needed or when
paralleling those in Figure 2. the correlative methods are not applicable.
Lubricants in Refrigerant Systems 7.7

Pour Point Table 4 Increase in Vapor Pressure and Temperature

Any lubricant intended for low-temperature service should be Vapor Pressure 32 mm2/s Oil
Temperature,
able to flow at the lowest temperature that it will encounter. This °C Alkylbenzene, kPa Naphthene Base, kPa
requirement is usually met by specifying a suitably low pour point.
149 0.10 0.12
The pour point of a lubricant is defined as the lowest temperature at
163 0.21 0.26
which it will pour or flow, when tested according to the standard
method prescribed in ASTM D97. 177 0.45 0.50
The loss of fluidity at the pour point may manifest itself in two 191 0.89 0.95
ways. Naphthenic oils and synthetic lubricants usually approach the 204 1.73 1.74
pour point by a steady increase in viscosity. Paraffinic oils, unless 218 3.23 3.06
heavily dewaxed, tend to separate out a rigid network of wax crys- 232 5.83 5.24
tals, which may prevent the flow while still retaining unfrozen
liquid in the interstices. Pour points can be lowered by adding chem- lubricants, the type, boiling range, and viscosity are also factors
icals known as pour point depressants. These chemicals are believed influencing vapor pressure; naphthenic oils of a specific viscosity
to modify the wax structure, possibly by depositing a film on the grade generally show higher vapor pressures than paraffinic oils.
surface of each wax crystal, so that the crystals no longer adhere to The vapor pressure of a lubricant increases with increasing tem-
form a matrix, and do not interfere with the lubricant’s ability to perature, as shown in Table 4. In practice, the vapor pressure of a
flow. Pour point depressants are not suitable for use with haloge- refrigeration lubricant at an elevated temperature is negligible com-
nated refrigerants. pared with that of the refrigerant at that temperature. The vapor
Standard pour test values are significant in the selection of oils pressure of narrow boiling petroleum fractions can be plotted as
for ammonia and carbon dioxide systems, and any other system in straight line functions. If the lubricant’s boiling range and type are
which refrigerant and lubricant are almost totally immiscible. In known, standard tables may be used to determine the lubricant’s
such a system, any lubricant that gets into the low side is essentially vapor pressure up to 101.3 kPa at any given temperature (API 1970).
refrigerant free; therefore, the pour point of the lubricant itself
determines whether loss of fluidity, congealment, or wax deposition Aniline Point
will occur at low-side temperatures. Aniline, an aromatic compound, is more soluble in oils contain-
Because oil in the low-pressure side of halogenated refrigerant ing a greater quantity of similar compounds. The temperature at
systems contains significant amounts of dissolved refrigerant, the which a lubricant and aniline are mutually soluble is the lubricant’s
pour point test, which is conducted on pure oils and in air, is of little aniline point (ASTM D611). Therefore, the relative aromaticity of a
significance. The viscosity of the lubricant-refrigerant solutions at mineral oil can be determined by its solubility in aniline. In compar-
the low-side conditions and the wax separation (or floc test) are ing mineral oils, lower aniline points correspond to the presence of
important considerations. more naphthenic and/or aromatic molecules.
The pour point for a lubricant should not be confused with the Aniline point can also predict a mineral oil’s effect on elastomer
freezing point. Pour point is determined by exposing the lubricant to seal materials. Generally, a highly naphthenic lubricant swells a
a low temperature for a short time. Refrigeration lubricants will specific elastomer material more than a paraffinic lubricant. This is
solidify after long-term exposure to a low temperature, even if the caused by the greater solvency of aromatic and naphthenic com-
temperature is higher than the pour point. pounds present in a naphthenic lubricant. However, aniline point
Some refrigerant lubricants stored at a low temperature become gives only a general indication of lubricant-elastomer compatibility.
unstable. Typically, components of the lubricant separate and form Within a given class of elastomer material, lubricant resistance var-
crystals or deposits on the container. ies widely because of differences in compounding practiced by the
elastomer manufacturer. Finally, in some retrofit applications, a
Volatility—Flash and Fire Points high aniline point mineral oil may cause elastomer shrinkage and
Because the boiling ranges and vapor pressure data on lubricants possible seal leakage.
are not readily available, an indication of the volatility of a lubricant Elastomers in synthetic lubricants, such as alkylbenzenes,
is obtained from the flash and fire points (ASTM D92). These prop- polyalkylene glycols, and polyol esters, behave differently than
erties are normally not significant in refrigeration equipment. How- they do in mineral oils. For example, an alkylbenzene has an
ever, some refrigerants, such as sulfur dioxide, ammonia, and methyl aniline point lower than that of a mineral oil of the same viscosity
chloride, have a high ratio of specific heats (cp /cv) and consequently grade. However, the amount of swell in a chloroneoprene O ring is
have a high adiabatic compression temperature. These refrigerants generally less than that found with the mineral oil. For these rea-
frequently carbonize oils with low flash and fire points when operat- sons, lubricant-elastomer compatibility needs to be tested under
ing in high ambient temperatures. Carbonization of the lubricant can conditions anticipated in actual service.
also occur in some applications that use halogenated refrigerants and
require high compression ratios (such as domestic refrigerator-freez- Solubility of Refrigerants in Oils
ers operating in high ambient temperatures). Because such carbon- All gases are soluble to some extent in lubricants, and many
ization or coking of the valves is not necessarily accompanied by the refrigerant gases are highly soluble. The amount dissolved depends
general lubricant deterioration, the tendency of a lubricant to carbon- on the pressure of the gas and the temperature of the lubricant, on
ize is referred to as thermal instability as opposed to chemical insta- the nature of the gas, and on the nature of the lubricant. Because
bility. Some manufacturers circumvent such problems by using refrigerants are much less viscous than lubricants, any appreciable
paraffinic oils, which in comparison to naphthenic oils have higher amount in solution causes a marked reduction in viscosity.
flash and fire points. Others prevent them through appropriate design. Two refrigerants usually regarded as poorly soluble in mineral
oil are ammonia and carbon dioxide. Data showing the slight
Vapor Pressure absorption of these gases by mineral oil are given in Table 5. The
Vapor pressure is the pressure at which the vapor phase of a amount absorbed increases with increasing pressure and decreases
substance is in equilibrium with the liquid phase at a specified tem- with increasing temperature. In ammonia systems, where pres-
perature. The composition of the vapor and liquid phases (when sures are moderate, the 1% or less refrigerant that dissolves in the
not pure) influences the equilibrium pressure. With refrigeration lubricant should have little, if any, effect on lubricant viscosity.
7.8 2002 ASHRAE Refrigeration Handbook (SI)

Table 5 Absorption of Low Solubility Refrigerant Gases in Oil The vapor pressure of a lubricant-refrigerant solution is markedly
Ammoniaa (Percent by Mass)
lower than that of the pure refrigerant. Consequently, the evaporator
temperature is higher than if the refrigerant is pure. Another result
Absolute Temperature, °C is what is sometimes called the flooded start-up. When the crank-
Pressure, kPa 0 20 65 100 140 case and the evaporator are at about the same temperature, the fluid
98 0.246 0.180 0.105 0.072 0.054 in the evaporator (which is mostly refrigerant) has a higher vapor
196 0.500 0.360 0.198 0.144 0.108 pressure than the fluid in the crankcase (which is mostly lubricant).
294 0.800 0.540 0.304 0.228 0.166 This difference in vapor pressures drives the refrigerant to the
393 — 0.720 0.398 0.300 0.222
crankcase and it is absorbed in the lubricant until the pressures are
equalized. At times, the moving parts in the crankcase may be com-
979 — — 1.050 0.720 0.545 pletely immersed in this lubricant-refrigerant solution. At start-up,
Carbon Dioxideb (Percent by Mass) the change in pressure and turbulence can cause excessive amounts
Absolute Temperature, °C of liquid to enter the cylinders, causing damage to the valves and
Pressure, kPa 0 20 65 100 starving the crankcase of lubricant. The use of crankcase heaters to
101 0.26 0.19 0.13 0.10 prevent such problems caused by highly soluble refrigerants is dis-
aType of oil: Not given (Steinle 1950)
cussed in Chapter 2 and by Neubauer (1958). The problems associ-
bType of oil: HVI oil, 34.8 mm2/s at 38°C (Baldwin and Daniel 1953) ated with rapid outgassing from the lubricant are more pronounced
with synthetic oils than with mineral oils. Synthetic oils release
absorbed refrigerant more quickly and have a lower surface tension,
However, operating pressures in CO2 systems tend to be much which results in a lack of stable foam found with mineral oils (Swal-
higher (not shown in Table 5), and in that case, the quantity of gas low et al. 1995).
dissolved in the lubricant may be enough to substantially reduce
viscosity. At 2.7 MPa, for example, Beerbower and Greene (1961) Density
observed a 69% reduction when a 32 mm2/s lubricant (HVI) was
When estimating the density of a lubricant-refrigerant solution,
tested under CO2 pressure at 27°C.
the solution is assumed ideal so that the specific volumes of the
components are additive. The formula for calculating the ideal den-
LUBRICANT-REFRIGERANT SOLUTIONS sity (ρid ) is
Many chlorinated refrigerants are highly soluble in oils at any
temperature likely to be encountered. The only limit to the amount ρo
of these refrigerants that the lubricant can dissolve is established by ρ id Z -------------------------------------------- (2)
1 H W ( ρo ⁄ ρR Ó 1 )
the refrigerant pressure at a given temperature. Chlorinated refrig-
erants such as R-22 and R-114 may show limited solubilities with
some lubricants at evaporator temperatures (exhibited in the form of where
phase separation) and unlimited solubilities in the higher tempera- ρo = density of pure lubricant at the solution temperature
ture regions of a refrigerant system. In some systems using HFC ρR = density of refrigerant liquid at the solution temperature
refrigerants, a second, distinct two-phase region may occur at high W = mass fraction of refrigerant in solution
temperatures. For such refrigerants, solubility studies must there- Depending on the refrigerant, the actual density of a lubricant-
fore be carried out over an extended temperature range. refrigerant solution may deviate from the ideal by as much as 8%.
Because halogenated refrigerants have such high solubilities, the The solutions are usually more dense than calculated, but some-
lubricating fluid can no longer be treated as a pure lubricant, but times they are less. For example, R-11 forms ideal solutions with
rather as a lubricant-refrigerant solution whose properties are mark- oils, whereas R-12 and R-22 show significant deviations. Density
edly different from those of pure lubricant. The amount of refriger- correction factors for R-12 and R-22 solutions are depicted in Fig-
ant dissolved in a lubricant depends on the pressure and ure 3. The corrected densities can be obtained from the relation
temperature. Therefore, the composition of the lubricating fluid is
different in different sections of a refrigeration system operating at ρ id
steady state and changes from the time of start-up until the system Mixture Density Z ρ m Z ------- (3)
attains the steady state. The most pronounced effect is on viscosity. A
The crankcase of a compressor can be used as an example. For
where A is the density correction factor read from Figure 3 at the
this case, the refrigerant and lubricant are assumed to be in equilib-
desired temperature and refrigerant concentration.
rium and the viscosity is as shown in Figure 37. If the lubricant in
the crankcase at start-up is 24°C, the viscosity of pure 32 ISO VG Van Gaalen et al. (1990, 1991a, 1991b) provide values of density
branched acid polyol ester is about 60 mm2/s. Under operating for four refrigerant/lubricant pairs: R-22/mineral oil, R-22/ alkyl-
conditions, the lubricant in the crankcase is typically about 52°C. At benzene, R-502/mineral oil, and R-502/alkylbenzene. Figures 4, 5,
this temperature the viscosity of the pure lubricant is about 6, and 7 provide data on the variation of density with temperature for
20 mm2/s. If R-134a is the refrigerant and the pressure in the crank- R-134a in combination with a 32 ISO VG polyol ester, a 100 ISO
case is 352 kPa, the viscosity of the lubricant-refrigerant mixture at VG polyol ester, a 32 ISO VG polyalkylene glycol, and an 80 ISO
start-up is about 10 mm2/s and decreases to 9 mm2/s at 52°C. VG polyalkylene glycol, respectively (Cavestri 1993).
Hence, if only lubricant properties are considered, an erroneous Cavestri (1993) provides density data as a function of tempera-
picture of the system is obtained. As another example, when the ture and pressure for R-134A/polyol ester oils as shown in Figures
lubricant returns from the evaporator to the compressor, the highest 4 through 7. Additionally, Cavestri and Schafer (2000) provide den-
viscosity does not occur at the lowest temperature, because the sity data as a function of temperature and pressure R-410A/ polyol
lubricant contains a large amount of dissolved refrigerant. As the ester oils as shown in Figures 8 through 11.
temperature increases, the lubricant loses some of the refrigerant
and the viscosity reaches a maximum at a point away from the cold- Thermodynamics and Transport Phenomena
est spot in the system. Dissolving lubricant in liquid refrigerant affects the thermo-
Similar to the lubricating fluid, the properties of the working dynamic properties of the working fluid. The vapor pressures of
fluid (a high refrigerant concentration solution) are also affected. refrigerant-lubricant solutions at a given temperature are always
Lubricants in Refrigerant Systems 7.9

Fig. 3 Density Correction Factors

Fig. 3 Density Correction Factors

(Loffler 1959)
Fig. 4 Density as Function of Temperature and Pressure for Fig. 5 Density as Function of Temperature and Pressure for
Mixture of R-134a and 32 ISO VG Mixture of R-134a and 100 ISO VG
Branched Acid Polyol Ester Lubricant Branched Acid Polyol Ester Lubricant

Fig. 4 Density as Function of Temperature and Pressure for

Mixture of R-134a and 32 ISO VG
Branched Acid Polyol Ester Lubricant Fig. 5 Density as Function of Temperature and Pressure for
Mixture of R-134a and 100 ISO VG
Branched Acid Polyol Ester Lubricant
less than the vapor pressure of pure refrigerant at that temperature.
Therefore, dissolved lubricant in an evaporator leads to lower suc- although a mixture of several compounds, may be considered one
tion pressures and higher evaporator temperatures than those component, and the refrigerant the other. The two phases are the
expected from pure refrigerant tables. Bambach (1955) gives an en- liquid phase and the vapor phase. The phase rule defines this mix-
thalpy diagram for R-12/lubricant solutions over the range of com- ture as having two degrees of freedom. Normally, the variables
positions from 0 to 100% lubricant and temperatures from −40 to involved are pressure, temperature, and the compositions of the
115°C. Spauschus (1963) developed general equations for calculat- liquid and of the vapor. Since the vapor pressure of the lubricant is
ing thermodynamic functions of refrigerant-lubricant solutions and negligible compared with that of the refrigerant, the vapor phase is
applied them to the special case of R-12/mineral oil solutions. essentially pure refrigerant, and only the composition of the liquid
phase needs to be considered. If the pressure and temperature are
Pressure-Temperature-Solubility Relations defined, the system is invariant (i.e., the liquid phase can have only
When a refrigerant is in equilibrium with a lubricant, a fixed one composition). This is a different but more precise way of stat-
amount of refrigerant is present in the lubricant at a given tempera- ing that a lubricant-refrigerant mixture having a known composi-
ture and pressure. This is evident if the Gibbs phase rule is applied tion exerts a certain vapor pressure at a certain temperature. If the
to basically a two-phase, two-component mixture. The lubricant, temperature is changed, the vapor pressure also changes.
7.10 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 6 Density as Function of Temperature and Fig. 9 Density as Function of Temperature and
Pressure for Mixture of R-134a and Pressure for Mixture of R-410A and
32 ISO VG Polypropylene Glycol 68 ISO VG Branched Acid
Butyl Ether Lubricant Polyol Ester Lubricant

Fig. 9 Density as Function of Temperature and

Fig. 6 Density as Function of Temperature and Pressure for Mixture of R-410A and
Pressure for Mixture of R-134a and 68 ISO VG Branched Acid
32 ISO VG Polypropylene Glycol Polyol Ester Lubricant
Butyl Ether Lubricant

Fig. 7 Density as Function of Temperature and Fig. 10 Density as Function of Temperature and
Pressure for Mixture of R-134a and Pressure for Mixture of R-410A and
80 ISO VG Polyoxypropylene 32 ISO VG Mixed Acid
Glycol Diol Lubricant Polyol Ester Lubricant

Fig. 7 Density as Function of Temperature and Fig. 10 Density as Function of Temperature and
Pressure for Mixture of R-134a and Pressure for Mixture of R-410A and
80 ISO VG Polyoxypropylene 32 ISO VG Mixed Acid
Glycol Diol Lubricant Polyol Ester Lubricant

Fig. 8 Density as Function of Temperature

and Pressure for Mixture of R-410A Fig. 11 Density as Function of Temperature
and 32 ISO VG Branched Acid and Pressure for Mixture of R-410A
Polyol Ester Lubricant and 68 ISO VG Mixed Acid
Polyol Ester Lubricant

Fig. 8 Density as Function of Temperature Fig. 11 Density as Function of Temperature

and Pressure for Mixture of R-410A and Pressure for Mixture of R-410A
and 32 ISO VG Branched Acid and 68 ISO VG Mixed Acid
Polyol Ester Lubricant Polyol Ester Lubricant
Lubricants in Refrigerant Systems 7.11

Fig. 12 P-T-S Diagram for Completely Miscible Refrigerants are classified as completely miscible, partially mis-
Refrigerant-Lubricant Solutions cible, or immiscible, according to their mutual solubility relations
with mineral oils. Because several commercially important refrig-
erants are partially miscible, further designation as having high,
intermediate, or low miscibility is shown in Table 6.
Completely miscible refrigerants and lubricants are mutually
soluble in all proportions at any temperature encountered in a refrig-
eration or air-conditioning system. This type of mixture always
forms a single liquid phase under equilibrium conditions, no matter
how much refrigerant or lubricant is present.
Partially miscible refrigerant-lubricant solutions are mutually
soluble to a limited extent. Above the critical solution temperature
(CST) or consolute temperature, many refrigerant/lubricant mix-
tures in this class are completely miscible, and their behavior is
identical to that just described. As mentioned previously, R-134a
and some synthetic lubricants exhibit a region of immiscibility at
higher temperatures.
Below the critical solution temperature, however, the liquid may
separate into two phases. Such phase separation does not mean that
the lubricant and the refrigerant are insoluble in each other. Each
liquid phase is a solution; one is lubricant-rich and the other
refrigerant-rich, depending on the predominant component. Each
phase may contain substantial amounts of the leaner component,
and these two solutions are themselves immiscible with each other.
The importance of this concept is best illustrated by R-502, which
is considered a low miscibility refrigerant exhibiting a high CST as
well as a broad immiscibility range. However, even at −20°C, the
lubricant-rich phase contains about 20 mass % of dissolved refriger-
ant (see Figure 15). Examples of partially miscible systems, in addi-
Fig. 12 P-T-S Diagram for Completely Miscible tion to R-502, are R-22, R-114, and R-13 with mineral oils.
Refrigerant-Lubricant Solutions The basic properties of the immiscible region can be recognized
by applying the phase rule. With three phases (two liquid and one
vapor) and two components, there can be only one degree of free-
Table 6 Mutual Solubility of Refrigerants and Mineral Oil dom. Therefore, either the temperature or the pressure automati-
Partially Miscible cally determines the composition of both liquid phases. If the
system pressure is changed, the temperature of the system changes
Completely High Intermediate Low and the two liquid phases assume somewhat different compositions
Miscible Miscibility Miscibility Miscibility Immiscible
determined by the new equilibrium conditions.
R-11 R-123 R-22 R-13 Ammonia Figure 13 illustrates the behavior of partially miscible mix-
R-12 R-114 R-14 CO2 tures. Point C on the graph represents the critical solution tem-
R-113 R-115 R-134a perature t 3 . There are three separate regions below this
R-152a R-407C temperature on the diagram. Reading from left to right, a family
of the smooth solid curves represents a region of completely mis-
R-C318 R-410A
cible lubricant-rich solutions. These curves are followed by a
R-502 wide break representing a region of partial miscibility in which
there are two immiscible liquid phases. On the right side, the par-
tially miscible region disappears into a second completely misci-
Pressure-temperature-solubility relations are usually presented ble region of refrigerant-rich solutions. A dome-shaped envelope
in the form shown in Figure 12. On this graph, P1° and P2° represent (broken line curve OCR) encloses the partially miscible region;
the saturation pressures of the pure refrigerant at temperatures t1 and everywhere outside this dome the refrigerant and lubricant are
t2, respectively. Point E1 represents an equilibrium condition, where completely miscible. In a sense, Figure 13 is a variant of Figure
one and only one composition of the liquid, represented by W1, is 12 in which the partial miscibility dome (OCR) blots out a sub-
possible at the pressure P1. If the temperature of this system is stantial portion of the continuous solubility curves. Under the
increased to t2, some of the liquid refrigerant evaporates, and the dome (i.e., in the immiscible region), the two points E1 and E2 on
equilibrium point shifts to E2, corresponding to a new pressure P2. the temperature line t 1 represent the two phases coexisting in
In either case, the lubricant-refrigerant solution exerts a vapor pres- equilibrium.
sure less than that of the pure refrigerant at the same temperature. These two phases differ considerably in composition (W1 and
W2) but have the same refrigerant pressure P1. The solution pres-
Mutual Solubility sure P1 lies not far below the saturation pressure of pure refrigerant
In a compressor, the lubricating fluid is a solution of refrigerant P1°. Commonly, refrigerant-lubricant solutions near the partial
dissolved in lubricant. In other parts of the refrigerant system, the miscibility limit show less reduction in refrigerant pressure than is
solution is a lubricant in liquid refrigerant. In both instances, either observed at the same lubricant concentration with completely mis-
the lubricant or the refrigerant could exist alone as a liquid if the cible refrigerants.
other were not present; therefore, any distinction between the dis- Totally immiscible lubricant-refrigerant solutions are de-
solving and dissolved component merely reflects a point of view. fined in this chapter as only very slightly miscible. In such mix-
Either of the liquids can be considered as dissolving the other. This tures, the immiscible range is so broad that mutual solubility
relationship is termed mutual solubility. effects can be ignored. Critical solution temperatures are seldom
7.12 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 13 P-T-S Diagram for Partially Miscible Fig. 14 P-T-S Relations of R-22 with 43 White Oil
Refrigerant-Oil Solutions (0% CA, 55% CN, 45% CP)

Fig. 14 P-T-S Relations of R-22 with 43 White Oil

(0% CA, 55% CN, 45% CP)
(Spauschus 1964)

Fig. 13 P-T-S Diagram for Partially Miscible

Refrigerant-Oil Solutions used or in systems involving very low evaporator temperatures
(Soling 1971).
Crankcase. With certain refrigerant and lubricant pairs, such as
R-502 and mineral oil, or even with R-22 in applications such as
found in mixtures of the totally immiscible type. Examples are
heat pumps, phase separation sometimes occurs in the crankcase
ammonia and lubricant, and carbon dioxide and mineral oil.
when the system is shut down. When this happens, the refrigerant-
Effects of Partial Miscibility in Refrigerant Systems rich layer settles to the bottom, often completely immersing the pis-
tons, bearings, and other moving parts. At start-up, the fluid that
Evaporator. The evaporator is the coldest part of the system and lubricates these moving parts is mostly refrigerant with little lubric-
the most likely part in which immiscibility or phase separation will ity, and severe bearing damage may result. The turbulence at start-
occur. If the evaporator temperature is below the critical solution up may cause the liquid refrigerant to enter the cylinders, carrying
temperature, phase separation is likely to occur in some part of the large amounts of lubricant with it. Precautions in design will prevent
evaporator. The fluid entering the evaporator is mostly liquid refrig- such problems in partially miscible systems.
erant containing a small fraction of lubricant, whereas the liquid Condenser. Partial miscibility is not a problem in the con-
leaving the evaporator is mostly lubricant, since the refrigerant is in denser, since the liquid flow lies in the turbulent region and the
vapor form. No matter how little lubricant the entering refrigerant temperatures are relatively high. Even if phase separation occurs,
carries, the liquid phase, as it progresses through the evaporator, there is little danger of separation of layers, the main obstacle to
passes through the critical composition which usually lies in 15% to efficient heat transfer.
20% lubricant in the total liquid phase.
Phase separation in the evaporator can sometimes cause prob-
Solubility Curves and Miscibility Diagrams
lems. In a dry-type evaporator, there is usually enough turbulence to
cause the phases to emulsify. In this case, the heat transfer character- Figure 14 shows mutual solubility relations of partially miscible
istics of the evaporator may not be significantly affected. In flooded- refrigerant-lubricant mixtures. More than one curve of this type can
type evaporators, however, the working fluid may separate into lay- be plotted on a miscibility diagram. Each single dome then repre-
ers, and the lubricant-rich phase may float on top of the boiling liq- sents the immiscible ranges for one lubricant and one refrigerant.
uid. In addition to the heat transfer, partial miscibility may also affect Miscibility curves for R-13, R-13B1, R-502 (Parmelee 1964), R-22,
the lubricant’s return from the evaporator to the crankcase. Usually and mixtures of R-12 and R-22 (Walker et al. 1957) are shown in
the lubricant is moved by high-velocity suction gas transferring Figure 15. Miscibility curves for R-13, R-22, R-502, and R-503 in
momentum to the droplets of lubricant on the return line walls. an alkylbenzene refrigeration lubricant are shown in Figure 16. A
If a lubricant-rich layer separates at the evaporator tempera- comparison with Figure 15 illustrates the greater solubility of refrig-
tures, this viscous, nonvolatile liquid can migrate and collect in erants in this type of lubricant.
pockets or blind passages not easily reached by the high-velocity
suction gas. The lubricant return problem may be magnified and, Effect of Lubricant Type on Solubility and Miscibility
in some cases, an oil logging can occur. The design of the system When compared on a mass basis, low-viscosity oils absorb
should take into account all these possibilities, and evaporators more refrigerant than high-viscosity oils do. Also, naphthenic oils
should be designed to promote entrainment (see Chapter 2). Oil absorb more than paraffinic oils. However, when compared on a
separators are frequently required in the discharge line to minimize mol basis, some confusion arises. Paraffinic oils absorb more
lubricant circulation when refrigerants of poor solvent power are refrigerant than naphthenic oils (i.e., reversal of the mass basis),
Lubricants in Refrigerant Systems 7.13

Fig. 15 Critical Solubilities of Refrigerants with 32 Naph- Fig. 16 Critical Solubilities of Refrigerants with 32 Alkylben-
thenic Lubricant (CA 12%, CN 44%, CP 44%) zene Lubricant

Fig. 15 Critical Solubilities of Refrigerants with 32

Naphthenic Lubricant (CA 12%, CN 44%, CP 44%) Fig. 16 Critical Solubilities of Refrigerants with 32
Alkylbenzene Lubricant
and there is little difference between a 15.7 mm2/s and a 64.7 mm2/s
naphthenic lubricant (Albright and Lawyer 1959; Albright and Loffler (1957) provides complete miscibility diagrams of R-22
Mandelbaum 1956). The differences on either basis are small (i.e., and 18 oils. A portion of the properties of the oils used and the crit-
within 20% of each other). Comparisons of oils by their carbon ical solution temperatures are summarized in Table 7. Although pre-
type analyses are not available, but in view of the data on naph- cise correlations are not evident in the table, certain trends are clear.
thenic and paraffinic types, differences between oils with different For the same viscosity grade and base, the effect of aromatic carbon
carbon type analyses, except perhaps for extreme compositions, content is seen in oils 2, 3, 7, and 8 and between oils 4 and 6. Sim-
are unlikely. ilarly, for the same viscosity grades, the effect of paraffinic structure
The effect of lubricant type and composition on miscibility is (with essentially the same % CA) is noticeable between oils 6 and 17
better defined than solubility. When the critical solution tempera- and between oils 8 and 18.
ture (CST) is used as the criterion of miscibility, oils with higher According to Loffler, the most pronounced effect on the critical
aromatic contents show a lower CST. Higher-viscosity-grade oils solution temperature is exerted by the aromatic content of the lubri-
show a higher CST than lower-viscosity-grade oils, and paraffinic cant; the table indicates that the paraffinic structure reduces the mis-
oils show a higher CST than naphthenic oils (see Figures 17 and 29). cibility compared with naphthenic structures. Sanvordenker (1968)
When the entire dome of immiscibility is considered, a similar reported the miscibility relations of the saturated fractions and the
result is noticeable. Oils that exhibit a lower CST usually show a aromatic fractions of mineral oils as a function of their physical prop-
narrowing of the immiscibility range (i.e., the mutual solubility is erties. The critical solution temperatures with R-22 increase with in-
greater at any given temperature). creasing viscosities for the saturates, as well as for the aromatics. For
equivalent viscosities, aromatic fractions with naphthenic linkages
Miscibility of R-22 with Lubricants show lower critical solution temperatures than aromatics with only
paraffinic linkages.
Parmelee (1964) showed that polybutyl silicate improves misci- Pate et al. (1993) developed miscibility data for 10 refrigerants
bility with R-22 (and also R-13) at low temperatures. Alkylben- and 14 lubricants. Table 8 lists lower and upper critical solution tem-
zenes, by themselves or mixed with mineral oils, also have better peratures for several of the refrigerant-lubricant pairs studied.
miscibility with R-22 than do mineral oils alone (Seeman and
Shellard 1963). Polyol esters, which are HFC miscible, are com-
pletely miscible with R-22 irrespective of viscosity grade. Solubilities and Viscosities of
For mineral oils, Walker et al. (1962) provide detailed miscibility Lubricant-Refrigerant Solutions
diagrams of 12 brand-name oils commonly used for refrigeration Although the differences are small on a mass basis, naphthenic
systems. Walker’s data show that in every case, higher-viscosity oils are better solvents than paraffinic oils. When considering the
lubricant of the same base and type has a higher critical solution viscosity of lubricant-refrigerant mixtures, naphthenic oils show
temperature. greater viscosity reduction than paraffinic oils for the same mass
7.14 2002 ASHRAE Refrigeration Handbook (SI)

Table 7 Critical Miscibility Values of R-22 with Different Oils

Carbon-Type Composition
Oil Oil Base Approximate Viscosity Viscosity at 50°C Critical Solution
No. Typea Grade, mm2/s (Converted), mm2/s %CA %CN %CP Temperature, °C
2 N 15 11.2 23 34 43 −37
3 N 15 10.2 2.5 48.5 49 −6
1 N 32 18.5 13 43 44 3
8 N 46 24.6 0.6 45 55 24
7 N 46 26.7 2.8 44 54 20
5 N 46+ 27.9 22 30 47 −16
4 N 46 28.6 26 28 46 –20
6 N 46 29.7 4 45 51 17
13 N 100 54.5 1.9 41 56 Noneb
12 N 100 60.7 4 41 55 Noneb
11 N 150 69.1 7 40 53 Noneb
10 N 220 93.2 21 27 52 16
9 N 220 109.0 27 24 50 9
18 P 46+ 29.3 0.5 33 67 Noneb
17 P 46 31.6 3.5 34 63 Noneb
16 P 68 35.2 6.4 30 63 Noneb
15 P 68 45.2 14.3 25 61 Noneb
14 P 100 50.0 18.1 22 60 44c
aP = Paraffinic, N = Naphthenic cAsecond (inverted) miscibility dome was observed above 58°C. Above this temperature, the oil/R-22 mix-
bNever completely miscible at any temperature ture again separated into two immiscible solutions.

Fig. 17 Effect of Oil Properties on Miscibility with R-22 Table 8 Critical Solution Temperatures for Selected
Refrigerant/Lubricant Pairs
Critical Solution
Temperature, °C
Refrig-
erant Lubricant Lower Upper
R-22 ISO 32 Naphthenic mineral oil −5 >60
ISO 32 Modified polyglycol −12 >60
ISO 68 Naphthenic mineral oil 15 >60
R-123 ISO 68 Naphthenic mineral oil −39 >60
ISO 58 Polypropylene glycol butyl monoether −50 14
R-134a ISO 58 Polypropylene glycol butyl monoether −50 56
ISO 32 Modified polyglycol 10 >90
ISO 22 Penta erythritol, mixed-acid ester −42 >90
ISO 58 Polypropylene glycol butyl monoether −46 6
ISO 100 Polypropylene glycol diol −46 11
ISO 100 Penta erythritol, mixed-acid ester −35 >32
ISO 100 Penta erythritol, branched-acid ester −46 12

percent of dissolved refrigerant. When the two effects are com-

pounded, under the same conditions of temperature and pressure, a
naphthenic lubricant in equilibrium with a given refrigerant shows a
significantly lower viscosity than a paraffinic lubricant.
Refrigerants also differ in their viscosity-reducing effects when
the solution concentration is measured in mass percent. However,
when the solubility is plotted in terms of mol percent, the reduction
in viscosity is approximately the same, at least for Refrigerants 13,
Compositions, % 13B1, 22, and 115 (Figure 18).
Oil No. Viscosity at , CA CN CP Ref. Spauschus (1964) reports numerical vapor pressure data on a
R-22/white oil system; solubility-viscosity graphs on naphthenic
1 34.0 12 44 44a 1
and paraffinic oils have been published by Loffler (1960), Little
2 33.5 7 46 47a 1 (1952), and Albright and Mandelbaum (1956). Some discrepancies,
3 63.0 12 44 44a 1 particularly at high R-22 contents, have been shown in data on
4 67.7 7 46 47a 1 viscosities that apparently could not be attributed to the properties
of the lubricant and remain unexplained. However, general plots
5 41.3 0 55 45 2 reported by the aforementioned authors are satisfactory for engi-
References: 1. Walker et al. (1957) 2. Spauschus (1964)
aEstimated composition, not in original reference.
neering and design purposes.
Spauschus and Speaker (1987) have compiled references of sol-
ubility and viscosity data. Selected solubility-viscosity data are
Fig. 17 Effect of Oil Properties on Miscibility with R-22 summarized in Figure 14 and Figures 19 through 31.
Lubricants in Refrigerant Systems 7.15

Fig. 18 Viscosity of Mixtures of Various Refrigerants Fig. 20 Viscosity-Temperature Chart for Solutions
and 32 Paraffinic Oil of R-22 in 32 Naphthene and
Paraffin Base Oils

Fig. 20 Viscosity-Temperature Chart for Solutions

of R-22 in 32 Naphthene and
Paraffin Base Oils

Fig. 21 Viscosity-Temperature Chart for Solutions

of R-22 in 65 Naphthene and
Paraffin Base Oils

Fig. 18 Viscosity of Mixtures of Various Refrigerants

and 32 Paraffinic Oil
(Albright and Lawyer 1959)

Fig. 19 Solubility of R-22 in 32 Naphthenic Oil

Fig. 21 Viscosity-Temperature Chart for Solutions

of R-22 in 65 Naphthene and
Paraffin Base Oils

Where possible, solubilities have been converted to mass percent

to provide consistency among the various charts. Figure 14 and Fig-
ures 19 through 23 contain data on R-22 and oils, Figure 24 on
R-502, Figures 25 and 26 on R-11, Figures 27 and 28 on R-12, and
Figures 29 and 30 on R-114. Figure 31 contains data on the solubil-
ity of various refrigerants in alkylbenzene lubricant. Viscosity-
solubility characteristics of mixtures of R-13B1 and lubricating oils
have been investigated by Albright and Lawyer (1959). Similar
studies on R-13 and R-115 are covered by Albright and Mandel-
baum (1956).
The solubility of refrigerants in oils, in particular of HFC refrig-
erants in ester oils, is usually determined experimentally. Wahl-
Fig. 19 Solubility of R-22 in 32 Naphthenic Oil strom and Vamling (2000) have developed a predictive scheme
7.16 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 22 Viscosity-Temperature Chart for Solutions of Fig. 23 Viscosity of Mixtures of 65 Paraffin

R-22 in 32 Naphthenic Oil Base Oil and R-22

Fig. 22 Viscosity-Temperature Chart for Solutions of

R-22 in 32 Naphthenic Oil
(Van Gaalen, et al. 1990 and 1991a)

based on group contributions that is predictive for the solubilities of

pentaerythritol esters and five HFCs ( HFC-125, HFC-134a, HFC-
143a, HFC-152a and HFC-32). The scheme uses a modified Flory-
Huggins model and a Unifac model. With these schemes, knowing Fig. 23 Viscosity of Mixtures of 65 Paraffin
only the structure of the pentaerythritol and the HFC refrigerant, the Base Oil and R-22
solubility can be predicted. (Albright and Mandelbaum 1956)

LUBRICANT RETURN FROM EVAPORATORS coldest regions in the evaporator, but at some intermediate point
Regardless of the miscibility relations of a lubricant with refrig- where much of the refrigerant has escaped from the lubricant. This
erants, for a refrigeration system to function properly, the lubricant condition is possibly in the suction line. The velocity of the return
must return adequately from the evaporator to the crankcase. vapor, which may be high enough to move the lubricant-refrigerant
Parmelee (1964) showed that the viscosity of the lubricant, solution in the colder part of the evaporator, may be too low to
saturated with refrigerant under low-pressure and low-temperature achieve the same result at the point of maximum viscosity. The
conditions, is important in providing good lubricant return. The vis- designer must consider this factor to minimize any lubricant return
cosity of the lubricant-rich liquid that accompanies the suction gas problems. Chapters 2 and 3 have further information on velocities in
changes as it sees rising temperatures on its way back to the com- return lines.
pressor. Two opposing factors then come into play. First, the in- Another aspect of viscosity data at the evaporator conditions is
creasing temperature tends to decrease the viscosity of the fluid. shown in Figure 35, which compares a synthetic alkylbenzene lubri-
Second, since the pressure remains unchanged, the increasing tem- cant with a naphthenic mineral oil. The two oils are the same vis-
perature also tends to drive off some of the dissolved refrigerant cosity grade, but the highly aromatic alkylbenzene lubricant has a
from the solution, thereby increasing its viscosity (Loffler 1960). much lower viscosity index in the pure state and shows a higher
Figures 32 through 34 show the variation in viscosity with tem- viscosity at low temperatures. However, at 135 kPa or approxi-
perature and pressure for three lubricant-refrigerant solutions rang- mately −40°C evaporator temperature, the viscosity of the lubri-
ing from −40°C to 21°C. In all cases, the viscosities of the solutions cant/R-502 mixture is considerably lower for alkylbenzene than for
passed through maximum values as the temperature was changed at naphthenic lubricant. In spite of the lower viscosity index, alkylben-
constant pressure, a finding that was also consistent with previous zene returns more easily than naphthenic lubricant.
data obtained by Bambach (1955) and Loffler (1960). According to Estimated viscosity-temperature-pressure relationships for a
Parmelee, the existence of a viscosity maximum is significant, naphthenic lubricant with R-502 are shown in Figure 36. Figures
because the lubricant-rich solution becomes most viscous not in the 37 and 38 show viscosity-temperature-pressure plots of alkylben-
Lubricants in Refrigerant Systems 7.17

Fig. 24 Solubility of R-502 in 32 Naphthenic Oil Fig. 26 Solubility of R-11 in 65 Oil

(CA 12%, CN 44%, CP 44%)

Fig. 24 Solubility of R-502 in 32 Naphthenic Oil

(CA 12%, CN 44%, CP 44%)
Fig. 26 Solubility of R-11 in 65 Oil

Fig. 25 Viscosity-Temperature Curves for Solutions of R-11 Fig. 27 Solubility of R-12 in Refrigerant Oils
in 65 Naphthene Base Oil

Fig. 25 Viscosity-Temperature Curves for Solutions of R-11

in 65 Naphthene Base Oil

zene and R-22 and R-502, respectively. These data are based on
experimental data from Van Gaalen et al. (1991a, 1991b). Figures
39 and 40 show viscosity-temperature-pressure data for mixtures of
R-134a and a 32 ISO VG polyalkylene glycol and an 80 ISO VG
polyalkylene glycol, respectively. Figures 41 and 42 show similar Solid lines: 32 naphthene base oil.
data for R-134a and a 32 ISO VG polyol ester and a 100 ISO VG Also 52 German base oil (Bambach 1955).
Broken lines: 32 and 70 mixed base oils.
polyol ester, respectively (Cavestri 1993). Cavestri and Schafer
(2000) provide viscosity data as a function of temperature and
pressure for R-410A/polyol ester oils as shown in Figures 43 Fig. 27 Solubility of R-12 in Refrigerant Oils
7.18 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 28 Viscosity-Temperature Chart for Solutions of Fig. 29 Critical Solution Temperatures

R-12 in 32 Naphthene Base Oil of R-114/Oil Mixtures

Fig. 28 Viscosity-Temperature Chart for Solutions of

R-12 in 32 Naphthene Base Oil Fig. 29 Critical Solution Temperatures
of R-114/Oil Mixtures

through 46. Viscosity and pressure data at constant concentrations Fig. 30 Solubility of R-114 in HVI Oils
are given in Figures 47 through 50.
Sundaresan and Radermacher (1996) observed oil return in a
small air-to-air heat pump. Three refrigerant lubricant pairs (R-22/
mineral oil, R-407C/mineral oil, and R-407C/polyol ester) were
studied under four conditions—steady-state cooling, steady-state
heating, cyclic operation, and a simulated lubricant pumpout situa-
tion. The lubricant returned rapidly to the compressor in the R-22/
mineral oil and R-407C/polyol ester tests, but oil return was unreli-
able in the R-407C/mineral oil test.
Kesim et al. (2000) developed general relationships for calculat-
ing the required refrigerant speed for carrying lubricant oil up ver-
tical sections of refrigerant lines. For these relationships they
assumed the thickness of the oil film to be 2% of the inner pipe
diameter. They converted these minimum speeds to the correspond-
ing refrigeration load or capacities for R-134a and copper suction
and discharge risers.

WAX SEPARATION (FLOC TESTS)

Wax separation properties are of little importance with synthetic
lubricants because they do not contain wax or wax-like molecules.
However, petroleum-derived lubricating oils are mixtures of large
numbers of chemically distinct hydrocarbon molecules. At low tem-
peratures in the low-pressure side of refrigeration units, some of the
larger molecules separate from the bulk of the lubricant, forming
wax-like deposits. This wax can clog capillary tubes and cause
expansion valves to stick, which is undesirable in refrigeration sys-
tems. Bosworth (1952) describes other wax separation problems.
In selecting a lubricant to use with completely miscible refrig-
erants, the wax-forming tendency of the lubricant can be deter-
mined by the floc test. The floc point is the highest temperature
at which wax-like materials or other solid substances precipitate
when a mixture of 10% lubricant and 90% R-12 is cooled under
specific conditions. Because different refrigerant and lubricant Fig. 30 Solubility of R-114 in HVI Oils
Lubricants in Refrigerant Systems 7.19

Fig. 31 Solubility of Refrigerants in 32 Fig. 33 Viscosity of R-22/Naphthenic Oil Solutions at

Alkylbenzene Oil Low-Side Conditions

Fig. 33 Viscosity of R-22/Naphthenic Oil Solutions at

Low-Side Conditions
(Parmelee 1964)

Fig. 34 Viscosity of R-502/Naphthenic Oil Solutions at

Low-Side Conditions

Fig. 31 Solubility of Refrigerants in 32

Alkylbenzene Oil

Fig. 32 Viscosity of R-12/Oil Solutions at Low-Side Condi-

tions

Fig. 34 Viscosity of R-502/Naphthenic Oil Solutions at

Low-Side Conditions

concentrations are encountered in actual equipment, test results

cannot be used directly to predict performance. The lubricant
concentration in the expansion devices of most refrigeration and
air-conditioning systems is considerably less than 10%, resulting
in significantly lower temperatures at which wax separates from
lubricant-refrigerant mixture. ASHRAE Standard 86 describes a
standard method of determining the floc characteristics of refrig-
eration oils in the presence of R-12.
Attempts to develop a test for the floc point of partially miscible
refrigerants for use with R-22 have not been successful. The solu-
tions being cooled often separate into two liquid phases. Once
phase separation occurs, the components of the lubricant distribute
themselves into the lubricant-rich phase and the refrigerant-rich
phase in such a way that the highly soluble aromatics concentrate
into the refrigerant phase, while the less soluble saturates concen-
trate into the lubricant phase. The waxy materials stay dissolved in
the refrigerant-rich phase only to the extent of their solubility limit.
Fig. 32 Viscosity of R-12/Oil Solutions at Low-Side Conditions On further cooling, any wax that separates from the refrigerant-
(Parmelee 1964) rich phase migrates into the lubricant-rich phase. Therefore, a
7.20 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 35 Viscosities of Solutions of R-502 Fig. 37 Viscosity-Temperature-Pressure Chart for Solutions

with 32 mm2/s Naphthenic Oil of
(CA 12%, CN 44%, CP 44%) R-22 in 32 mm2/s Alkylbenzene Oil
and 32 mm2/s Synthetic Alkylbenzene Oil

Fig. 35 Viscosities of Solutions of R-502

with 32 mm2/s Naphthenic Oil
(CA 12%, CN 44%, CP 44%)
and 32 mm2/s Synthetic Alkylbenzene Oil

Fig. 36 Viscosity-Temperature-Pressure Chart for

Solutions of R-502 in
32 mm2/s Naphthenic Oil

Fig. 37 Viscosity-Temperature-Pressure Chart for Solutions of

R-22 in 32 mm2/s Alkylbenzene Oil

significant floc point cannot be obtained with partially miscible

refrigerants once phase separation has occurred. However, lack of
flocculation does not mean lack of wax separation. Wax may sepa-
rate in the lubricant-rich phase, causing it to congeal. Parmelee
(1964) reported such phenomena with a paraffinic lubricant and
R-22.
Floc point might not be reliable when applied to used oils. A part
of the original wax may already have been deposited, and the used
lubricant may contain extraneous material from the operating
equipment.
Good design practice suggests selecting oils that do not deposit
wax on the low-pressure side of a refrigeration system, regardless of
single-phase or two-phase refrigerant-lubricant solutions. Mechan-
ical design affects how susceptible equipment is to wax deposition.
Wax deposits at sharp bends and the suspended wax particles build
up on the tubing walls by impingement. Careful design avoids bends
and materially reduces the tendency to deposit wax.

SOLUBILITY OF
HYDROCARBON GASES
Hydrocarbon gases such as propane (R-290) and ethylene
(R-1150) are miscible with the compressor lubricating oil and are
absorbed by the lubricant. The lower the boiling point or critical
temperature, the less soluble the gas, all other values being equal.
Gas solubility increases with decreasing temperature and increasing
Fig. 36 Viscosity-Temperature-Pressure Chart for pressure (Figures 51 and 52). As with other lubricant miscible
Solutions of R-502 in refrigerants, absorption of the hydrocarbon gas reduces lubricant
32 mm2/s Naphthenic Oil viscosity.
Lubricants in Refrigerant Systems 7.21

Fig. 38 Viscosity-Temperature-Pressure Chart line carrying liquid refrigerant or in a line returning lubricant to the
for Solutions of R-502 in compressor. The material in the filter/dryer must be compatible with
32 mm2/s Alkylbenzene Oil the lubricant. Also, desiccants can remove some additives in the
lubricant.
Spot checks show that water solubility data for transformer oils
obtained by Clark (1940) also apply to refrigeration oils (Figure 53).
A simple method, previously used in industry to detect free water
in refrigeration oils, is the dielectric breakdown voltage (ASTM
D877), which is designed to control moisture and other contaminants
in electrical insulating oils. The method does not work with polyester
and polyalkylene glycol oils, however. According to Clark (1940),
the dielectric breakdown voltage decreases with increasing moisture
content at the same test temperature and increases with temperature
for the same moisture content. At 27°C, when the solubility of water
in a 32 mm2/s naphthenic lubricant is between 50 to 70 mg/kg, a
dielectric breakdown voltage of about 25 kV indicates that no free
water is present in the lubricant. However, the lubricant may contain
dissolved water up to the solubility limit. Therefore, a dielectric
breakdown voltage of 35 kV is commonly specified to indicate that
the moisture content is well below saturation.
The ASTM D877 test is not sensitive below about 60% satura-
tion. Current practice is to measure directly the total moisture con-
tent by procedures such as the Karl Fischer (ASTM D1533) method.

SOLUBILITY OF AIR IN LUBRICANTS

Refrigerant systems should not contain excessive amounts of
air or other noncondensable gases. Oxygen in air can react with the
lubricant to form oxidation products. More importantly, nitrogen
in the air (which does not react with lubricant) is a noncondensable
gas that can interfere with performance. In some systems, the tol-
erable volume of noncondensables is very low. Therefore, if the
lubricant is added after the system is evacuated, it must not contain
an excessive amount of dissolved air or other noncondensable gas.
Fig. 38 Viscosity-Temperature-Pressure Chart Dissolved air is removed when a vacuum is used to dry the lubri-
for Solutions of R-502 in cant. However, if the deaerated lubricant is stored under pressure
32 mm2/s Alkylbenzene Oil in dry air, it will reabsorb air in proportion to the pressure (Bald-
win and Daniel 1953). Dry nitrogen blankets are preferred over
using dry air for keeping lubricants dry because introducing air
SOLUBILITY OF WATER into a system can cause problems with unintended oxidation.
IN LUBRICANTS
Refrigerant systems must be dry internally because high mois- FOAMING AND ANTIFOAM AGENTS
ture content can cause ice to form in the expansion valve or capillary
tube, corrosion of bearings, reactions that affect the lubricant/refrig- Excessive foaming of the lubricant is undesirable in refrigeration
erant stability, or other operational problems. systems. Brewer (1951) suggests that abnormal refrigerant foaming
As with other components, the refrigeration lubricant must be as reduces the lubricant’s effectiveness in cooling the motor windings
dry as practical. Normal manufacturing and refinery handling prac- and removing heat from the compressor. Too much foaming also
tices result in a moisture content of about 30 mg/kg for almost all can cause too much lubricant to pass through the pump and enter the
hydrocarbon-based lubricants. Polyalkylene glycols generally low-pressure side. Foaming in a pressure oiling system can result in
contain several hundred mg/kg of water. Polyol esters usually con- starved lubrication under some conditions.
tain 50 to 100 mg/kg moisture. However, this amount may increase However, moderate foaming is beneficial in refrigeration sys-
between the time of shipment from the refinery and the time of tems, particularly for noise suppression. A foamy layer on top of the
actual use, unless proper preventive measures are taken. Small con- lubricant level dampens the noise created by the moving parts of the
tainers are usually sealed. Tank cars are not normally pressure compressor. Moderate foam also lubricates effectively, yet it is
sealed or nitrogen blanketed except for shipment of synthetic polyol pumpable, which minimizes the risk of vapor lock of the oil pump
ester and polyalkylene lubricants, which are quite hygroscopic. at start-up. There is no general agreement on what constitutes exces-
During transit, changes in ambient temperatures cause the lubri- sive foaming or how it should be prevented. Some manufacturers
cant to expand and contract and draw in humid air from outside. add small amounts of an antifoam agent, such as silicone fluid, to
Depending on the extent of such cycling, the moisture content of the refrigerator oils. Others believe that foaming difficulties are more
lubricant may be significantly higher than at the time of shipment. easily corrected by equipment design.
Users of large quantities of refrigeration oils frequently dry the Goswami et al. (1997) observed the foaming characteristics of
lubricant before use. Chapter 43 discusses the methods of drying R-32, R-125, R-134a, R-143a, R-404A, R-407C, and R-410A
lubricants. Normally, removing any moisture present will also with two ISO 68 polyol ester lubricants. They compared them to
deaerate the lubricant. R-12 and R-22 paired with both an ISO 32 and ISO 68 mineral oil
Because POE and PAG lubricants are quite hygroscopic, when and found that the foamability and foam stability of the HFC/
they are in a refrigeration system they should circulate through a POE pairs were much lower than those of the R-12 and R-22/
filter/dryer designed for liquids. A filter/dryer can be installed in the mineral oil pairs.
7.22 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 39 Viscosity-Temperature-Pressure Plot for 32 ISO VG Polypropylene Glycol Butyl Mono Ether with R-134a

Fig. 39 Viscosity-Temperature-Pressure Plot for 32 ISO VG Polypropylene Glycol Butyl Mono Ether with R-134a

Fig. 40 Viscosity-Temperature-Pressure Plot for 80 ISO VG Polyoxypropylene Diol with R-134a

Fig. 40 Viscosity-Temperature-Pressure Plot for 80 ISO VG Polyoxypropylene Diol with R-134a

Lubricants in Refrigerant Systems 7.23

Fig. 41 Viscosity-Temperature-Pressure Plot for 32 ISO VG Branched Acid Polyol Ester with R-134a

Fig. 41 Viscosity-Temperature-Pressure Plot for 32 ISO VG Branched Acid Polyol Ester with R-134a

Fig. 42 Viscosity-Temperature-Pressure Plot for 100 ISO VG Branched Acid Polyol Ester with R-134a

Fig. 42 Viscosity-Temperature-Pressure Plot for 100 ISO VG Branched Acid Polyol Ester with R-134a
7.24 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 43 Viscosity-Temperature-Pressure Plot Fig. 46 Viscosity-Temperature-Pressure Plot

for a Mixture of R-410A and 32 ISO VG Mixed Acid for a Mixture of R-410A and 68 ISO VG Branched Acid
Polyol Ester Lubricant Polyol Ester Lubricant

Fig. 43 Viscosity-Temperature-Pressure Plot Fig. 46 Viscosity-Temperature-Pressure Plot

for a Mixture of R-410A and 32 ISO VG Mixed Acid for a Mixture of R-410A and 68 ISO VG Branched Acid
Polyol Ester Lubricant Polyol Ester Lubricant
Fig. 44 Viscosity-Temperature-Pressure Plot Fig. 47 Viscosity as a Function of Temperature and
for a Mixture of R-410A and 68 ISO VG Mixed Acid Pressure at Constant Concentrations for a Mixture of R-410A
Polyol Ester Lubricant and 32 ISO VG Mixed Acid Polyol Ester Lubricant

Fig. 44 Viscosity-Temperature-Pressure Plot Fig. 47 Viscosity as a Function of Temperature and

for a Mixture of R-410A and 68 ISO VG Mixed Acid Pressure at Constant Concentrations for a Mixture of R-410A
Polyol Ester Lubricant and 32 ISO VG Mixed Acid Polyol Ester Lubricant

Fig. 45 Viscosity-Temperature-Pressure Plot Fig. 48 Viscosity as a Function of Temperature and

for a Mixture of R-410A and 32 ISO VG Branched Acid Pressure at Constant Concentrations for a Mixture of R-410A
Polyol Ester Lubricant and 68 ISO VG Mixed Acid Polyol Ester Lubricant

Fig. 45 Viscosity-Temperature-Pressure Plot Fig. 48 Viscosity as a Function of Temperature and

for a Mixture of R-410A and 32 ISO VG Branched Acid Pressure at Constant Concentrations for a Mixture of R-410A
Polyol Ester Lubricant and 68 ISO VG Mixed Acid Polyol Ester Lubricant

moisture, or any other contaminant. Oxidation resistance by itself

OXIDATION RESISTANCE is rarely included in refrigeration lubricant specifications.
Refrigeration oils are seldom exposed to oxidizing conditions in Nevertheless, oxidation tests are justified, because oxidation
hermetic systems. Once a system is sealed against air and mois- reactions are chemically similar to the reactions between oils and re-
ture, the oxidation resistance of a lubricant is not significant unless frigerants. An oxygen test, using power factor as the measure,
it reflects the chemical stability. Handling and manufacturing correlates with established sealed-tube tests. However, such oxida-
practices include elaborate care to protect lubricants against air, tion resistance tests are not used as primary criteria of chemical
Lubricants in Refrigerant Systems 7.25

Fig. 49 Viscosity as a Function of Temperature and Fig. 51 Solubility of Propane in Oil

Pressure at Constant Concentrations for a Mixture of R-410A
and 32 ISO VG Branched Acid Polyol Ester Lubricant

Fig. 49 Viscosity as a Function of Temperature and

Pressure at Constant Concentrations for a Mixture of R-410A
and 32 ISO VG Branched Acid Polyol Ester Lubricant
Fig. 50 Viscosity as a Function of Temperature and
Pressure at Constant Concentrations for a Mixture of R-410A
and 68 ISO VG Branched Acid Polyol Ester Lubricant

Fig. 51 Solubility of Propane in Oil

evaluating the chemical stability of lubricant-refrigerant mixtures
are covered in Chapter 5.
Various phenomena in an operating system, such as sludge for-
Fig. 50 Viscosity as a Function of Temperature and mation, carbon deposits on valves, gumming, and copper plating of
Pressure at Constant Concentrations for a Mixture of R-410A bearing surfaces, have been attributed to lubricant decomposition in
and 68 ISO VG Branched Acid Polyol Ester Lubricant the presence of the refrigerant. In addition to the direct reactions of
the lubricant and refrigerant, the lubricant may also act as a medium
reactivity, but rather to support the claims of chemical stability de- for reactions between the refrigerant and the motor insulation, par-
termined by sealed-tube and other tests. ticularly when the refrigerant extracts the lighter components of the
Oxidation resistance may become a prime requirement during insulation. Factors affecting the stability of various components
manufacture. The small amount of lubricant used during compres- such as wire insulation materials in hermetic systems are also cov-
sor assembly and testing is not always completely removed before ered in Chapter 5.
the system is dehydrated. If the subsequent dehydration process is
carried out in a stream of hot, dry air, as is frequently the case, the Effect of Lubricant Type
hot oxidizing conditions can cause the residual lubricant to become
gummy, leading to stuck bearings, overheated motors, and other Mineral oils differ in their ability to withstand chemical attack by
operating difficulties. For these purposes, the lubricant should have a given refrigerant. In an extensive laboratory sealed-tube test pro-
high oxidation resistance. However, the lubricant used under such gram, Walker et al. (1960, 1962) showed that color darkening, cor-
extreme conditions should be classed as a specialty process lubri- rosion of metals, deposits, and copper plating occur less in
cant rather than a refrigeration lubricant. paraffinic oils than in naphthenic oils. Using gas analysis, Spaus-
chus and Doderer (1961) and Doderer and Spauschus (1965) show
that a white oil containing only saturates and no aromatics is con-
CHEMICAL STABILITY siderably more stable in the presence of R-12 and R-22 than a
Refrigeration lubricants must have excellent chemical stability. medium-refined lubricant is. Steinle (1950) reported the effect of
Within the enclosed refrigeration environment, the lubricant must oleoresin (nonhydrocarbons) and sulfur content on the reactivity of
resist chemical attack by the refrigerant in the presence of all the the lubricant, using the Philipp test. A decrease in the oleoresin con-
materials encountered, including the various metals, motor insula- tent, accompanied by a decrease in sulfur and aromatic content,
tion, and any unavoidable contaminants trapped in the system. The showed an improvement in the chemical stability with R-12, while
presence of air and water is the most common cause of problems the oil’s lubricating properties became poorer. Schwing’s (1968)
with the chemical stability of lubricants in refrigeration and air- study on a synthetic polyisobutyl benzene lubricant reports that it is
conditioning systems. This is true for all lubricants, especially for not only chemically stable but also has good lubricating properties.
polyol esters and to some extent for polyalkylene glycols. Lubricant HFC refrigerants are chemically very stable and show very little
might react with a chlorine-containing refrigerant at elevated tem- tendency to degrade under conditions found in refrigeration and air-
peratures, and the reaction can be catalyzed by metals. Methods for conditioning systems. HFC refrigerants are therefore not a factor in
7.26 2002 ASHRAE Refrigeration Handbook (SI)

Fig. 52 Solubility of Ethylene in Oil Fig. 53 Solubility of Water in Mineral Oil

Fig. 53 Solubility of Water in Mineral Oil

kits or portable refractometers are available to determine the amount

of old lubricant that is mixed with the flushed material.

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