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International Journal of Refrigeration 27 (2004) 346–352

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Concentration measurement of refrigerant/refrigeration oil


mixture by refractive index
Mitsuhiro Fukuta*, Tadashi Yanagisawa, Satoshi Miyamura, Yasuhiro Ogi
Department of Mechanical Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu, 432-8561, Japan

Received 15 August 2003; received in revised form 20 November 2003; accepted 24 December 2003

Abstract
Refrigeration oil having good miscibility with refrigerant is generally used in refrigeration units. Precise measure-
ment of the mixing ratio of refrigerant to refrigeration oil is required for a sufficient understanding of the refrigeration
cycle. In this paper, refractive index is chosen as a property which indicates the mixing concentration of the refrigerant/
oil mixture. A laser displacement sensor is used to detect a change of optical path which changes according to the
refractive index of test medium. The refractive indices of pure refrigerant, pure refrigeration oil and refrigerant/refrig-
eration oil mixture are measured with several combination of refrigerant/oil. It is found that the difference of refractive
index between the refrigerant and the oil is sufficient for the measurement of the mixing concentration of refrigerant/oil
mixture, and that the refractive index of the refrigerant/oil mixture changes almost linearly according to the mixing
concentration. These data will be utilized for development of an in situ sensor in refrigerant compressors.
# 2004 Elsevier Ltd and IIR. All rights reserved.
Keywords: Mesurment; Concentration; Refrigerant; Mixture; Lubricant; Refractive index

Mesures des concentrations en frigorigène/lubrifiant de


mélanges à l’aide de l’indice de réfraction
Mots cle´s : Mesure ; Concentration ; Frigorigène ; Mélange ; Lubrifiant ; Indice de réfraction

1. Introduction increases, the viscosity of lubricant decreases sig-


nificantly and it causes changes of lubrication char-
In general, refrigeration oil of good solubility with acteristics and sealing ones in a compression chamber.
refrigerant is used in refrigeration compressors. The In addition, the oil concentration in the refrigerant cir-
solubility changes according to the pressure and the culating in the cycle, which is termed the oil circulation
temperature and it influences the performance or relia- ratio, affects the pressure drop and the heat transfer in
bility of the compressor as well as the operation of the heat exchangers. The measurement of the concentration
cycle. For example, when the concentration of refriger- of refrigerant in the oil or the oil circulation ratio,
ant in the refrigeration oil stored in the compressor therefore, is very important to improve cycle perfor-
mance and to ensure the reliability of the system. The
most general way to measure the concentration of
* Corresponding author. Tel.: +81-53-478-1054; fax: +81- refrigerant/oil mixture is a sampling method [1], but the
53-478-1058. measurement is time consuming and reduces the amount
E-mail address: tmmfuku@ipc.shizuoka.ac.jp (M. Fukuta). of oil in the compressor or cycle. Although one can
0140-7007/$35.00 # 2004 Elsevier Ltd and IIR. All rights reserved.
doi:10.1016/j.ijrefrig.2003.12.007
M. Fukuta et al. / International Journal of Refrigeration 27 (2004) 346–352 347

used in this study because the measurement can be done


Nomenclature relatively easily with high accuracy although it is not
suitable for miniaturization of the sensor.
d sensor output, m Fig. 1 shows the principle of the measurement. The
h depth of test medium, m test medium, refrigerant/oil mixture, is stored in the
‘ distance from sensor to glass, m pressurized chamber having a glass window. The inci-
n refractive index dent light enters the test medium through the glass and
t glass thickness reflects off the surface of a base plate. When the incident
x distance, m beam passes through interfaces between air and
 angle of optical path, rad the glass, and between the glass and the test medium,
the refraction occurs because of different refractive
Subscript indices of air, glass and test medium. The optical path
1 air changes according to the refractive index of the test
2 glass medium as shown in Fig. 1. In order to detect the
3 test medium change of optical path, a laser displacement sensor is
used in this study. The sensor is the diffusion reflection
type, which detects the diffusion light at the reflection
surface by collecting the light on a CCD with a com-
estimate the concentration based on the solubility data pound lens. However, when the incident light passes
by measuring the pressure and the temperature, there is through the liquid test medium, the diffusion reflection
no guarantee that the condition is always saturated or also occurs in the test medium and the diffusion reflec-
sometimes there is no solubility data from oil manu- tion on the surface is hardly detected. The sensor,
facturers. Because of such shortcomings of these meth- therefore, is used as a regular reflection type with an
ods, real-time measurements of the concentration of inclined position, which detects the regular reflection
refrigerant/oil mixture have been developed. beam as shown in Fig. 2. The regular reflection light
Certain sensors and principles for the real-time reflects with the same angle, , as the incident light on
measurement were proposed, which detect viscosity the base surface, then it is collected on the CCD by the
[2,3], acoustic velocity [2,4–8], density [2,8–10], absorp- lens. The sensor output shows the distance of d in Fig. 2.
tion of light [11–13] or dielectric constant [11,14].
Refractive index [11,15,16] is one of the properties
which changes according to the concentration of refrig-
erant/oil mixture. So far, however, no sufficient data of
the refractive index of the refrigerant/oil mixture has
been published. In this study, the refractive index of
refrigerant/oil mixture is measured by utilizing a laser
displacement sensor. The characteristics of a refractive
index sensor incorporating the displacement sensor, and
the change of refractive index against the concentration
of refrigerant/oil mixture are discussed. In addition, the Fig. 1. Principle of measurement.
influence of oil degradation on the measurement is dis-
cussed from the view point of practical applications of
the sensor to the cycle.

2. Experiment

2.1. Principle of measurement

The methods to detect the refractive index are classi-


fied mainly into three methods. One is to detect a
change of light intensity through a sensor [17,18], the
second is to detect a change of optical path [15,19,20]
and the third is to detect the critical angle [11,16,21].
The purpose of this study is to provide fundamental
data which is useful in the development of the sensor.
The method by detecting the optical path, therefore, is Fig. 2. Detection of regular reflection.
348 M. Fukuta et al. / International Journal of Refrigeration 27 (2004) 346–352

Fig. 4. Experimental setup.

Fig. 3. Actual and imaginary optical paths in sensor unit. measure the refractive index under the pressurized con-
dition. The specifications of the measuring unit are
designed so that the range of the refractive index of the
test medium from 1.0 to 1.5 corresponds to as wide a
Fig. 3 illustrates geometrically the actual optical path measuring range of the displacement sensor as possible.
and an imaginary one for the output of the sensor. The The measuring unit is connected to a mixing chamber
refraction angles follow Snell’s law as expressed by Eq. (1). with a stirrer and the test chamber is filled with the
n1 sin1 ¼ n2 sin2 ¼ n3 sin3 ð1Þ refrigerant/oil mixture. The temperature of test medium
is controlled by an electric heater with circulating the
where, n1, n2 and n3 are the refractive indices of air, glass test medium by a gear pump, and is measured by a
and test medium, i.e. refrigerant/oil mixture, and 1, 2 T-type thermocouple with the precision of 0.1  C. The
and 3 are the angles of light in each substance, respec- concentration of refrigerant/oil mixture is checked by
tively. In Fig. 3, the distance x is expressed as follows. the sampling method. In this paper, the refractive indi-
x ¼ 2ð‘tan1 þ ttan2 þ htan3 Þ ð2Þ ces of several refrigerants and oils are measured and
also the refractive indices of their mixtures are exam-
where ‘ is distance from the sensor to the glass surface, t ined. The refrigerants used in this study are R134a, R32,
is the glass thickness and h is depth of the test medium. R125, R410A and R600a, and the oils are PAG, PVE
The laser displacement sensor detects a reflection sur- and a paraffinic mineral oil. The concentration of
face at an imaginary point (A) in Fig. 3, then it outputs refrigerant ranges from 0 to 100% and the temperature
the distance d. The relationship between d and x is is from 30 to 50  C. In addition, the influence of oil
expressed by Eq. (3). degradation on the measurement is checked from the
x ¼ 2dsin1 ð3Þ view point of practical applications of the sensor to the
refrigeration cycle.
With reducing Eqs. (1)–(3), the relationship between
the refractive index of test medium, n3, and the sensor
output, d, is obtained. 3. Results and discussion
     
n1 n1
‘tan1 þttan sin1 sin1 þhtan sin1 sin1 3.1. Calibration of sensor
n2 n3

sin1
At first, the calibration of the sensor output against
ð4Þ the refractive index of the test medium is carried out by
using substances whose refractive indices are known.
2.2. Experimental setup The sensor output data obtained by the experiment and
the calculated one are plotted versus the refractive index
Fig. 4 shows the schematic diagram of experimental in Fig. 5. The refractive indices of alcohols, ethanol, 1-
setup. The laser displacement sensor used in this study propanol and isoamyl alcohol, are derived from a
has the measuring range from 25 to 35 mm with resolu- property table [22], those of refrigerants, R125, R32 and
tion of 1 mm. The laser is a semiconductor type and the R22, are obtained from Refs. [19] and [22] and those of
wave length is 670 nm. A refractive index sensor unit refrigeration oils, naphthenic mineral oil, PAG and
(measuring unit) consists of the laser displacement sen- PVE, are measured by a handy refractive index meter.
sor, the optical flat glass (BK7), the test medium cham- The refractive indices of the substances except the
ber and the reflection base plate, which enables to refrigerants are given by those with sodium yellow D-
M. Fukuta et al. / International Journal of Refrigeration 27 (2004) 346–352 349

line (589.3 nm) at 25  C, and those of the refrigerants of R134a and PAG oil against the temperature. The
are values under different conditions depending on each refractive index of R134a is about 1.19, whereas that of
literature. In Fig. 5, the sensor output is shown by the oil is about 1.45 and is much larger than that of the
relative value to that of air, and it decreases with refrigerant. In general, it is easy to measure the refrac-
increasing the refractive index. The measured sensor tive index with the precision of 1103 and the refrac-
output shows good agreement with that calculated by tive indices of R134a and PAG oil have enough
Eq. (4), although the measured value is slightly smaller difference for the measurement of the mixing concen-
than the calculated one. The deviation is caused by the tration. Over the temperature range in this study, the
compound lens which is not as simple as the one shown refractive index of R134a slightly decreases linearly with
in the previous figures, inaccurate angle at which the increasing the temperature. The refractive index of PAG
displacement sensor is mounted, lack of flatness of oil also decreases with the temperature, but it is less
the base plate, etc. In this study, the correlation sensitive to the temperature.
curve obtained by the experiment is used to convert the The refractive indices of a near azeotropic refrigerant,
sensor output to the refractive index. The slope of the R410A, and its components, R32 and R125, as well as
curve shows sensitivity of the refractive index sensor and that of PVE oil are shown against the temperature in
about 0.07/mm and 0.12/mm around the refractive Fig. 7. The refractive indices of R32, R125 and R410A
indices of 1.2 and 1.5, respectively. Since the resolution are slightly smaller than R134a’s shown in Fig. 6. The
of the laser displacement sensor is 1 mm, the uncertainty refractive index of R32 is about 0.01 greater than that of
of the refractive index sensor is less than 5104 taking R125, but the difference is negligible as compared with
into account the fluctuation of the output and error of that from the refractive index of PVE oil. Therefore,
the calibration curve. In the present design of the sensor even if a selective dissolution of R32 and R125 into the
arrangement, the measuring range of refractive index is refrigeration oil occurs, i.e. the concentrations of R32
from 1.0 to 1.5. If the design is changed so that the and R125 in the oil are different, the error of the refrig-
measuring range corresponds to the range from the erant concentration in the oil is less than 1% when it is
refractive index of refrigerant to that of refrigeration oil, considered as the overall refrigerant concentration.
i.e. 1.2–1.5, it will be possible to measure the refractive In recent years, R600a (isobutane) is used as a refrig-
index of refrigerant/oil mixture more accurately. erant in domestic refrigerators. Fig. 8 shows the refrac-
tive indices of R600a and the paraffinic mineral oil
3.2. Refractive indices of refrigerant and refrigeration oil which is used in the refrigerator with R600a on the
market. The refractive index of R600a is around 1.3 and
The concentration of refrigerant/oil mixture can be much larger than those of R134a and R410A. The
measured accurately as the difference between the refractive index of the paraffinic oil is around 1.47 and
refractive indices of refrigerant and oil is larger. The also larger than PAG’s and PVE’s. Although the differ-
refractive indices of pure refrigerant and pure oil, ence between the refractive indices of R600a and the
therefore, are measured for several combinations of paraffinic oil is smaller than that of the other com-
refrigerant and oil. Fig. 6 shows the refractive indices bination, it is enough to detect the concentration of

Fig. 5. Calibration curve. *: Ref. 19, **: Ref. 22. Fig. 6. Refractive indices of R134a and PAG oil.
350 M. Fukuta et al. / International Journal of Refrigeration 27 (2004) 346–352

refrigerant/oil mixture. The refractive indices of R600a


and the paraffinic oil have the same tendency against the
temperature as the other combinations.
The typical refractive indices of refrigerants and
refrigeration oils measured in this study are summarized
in Table 1 as a reference.

3.3. Refractive indices of refrigerant/oil mixture

Refractive indices of a few kinds of refrigerant/oil


mixtures were measured with varying the mass concen-
tration of refrigerant in the oil. Fig. 9 shows the rela-
tionship between the concentration of R134a in the
PAG oil and the refractive index with temperature as a
parameter. The refractive index of the mixture decreases
almost linearly with increasing the refrigerant concen-
tration. It means that the refractive index is a suitable
property to detect the concentration of the refrigerant/
Fig. 7. Refractive indices of R410A, R32, R125 and PVE oil.
oil mixture in the whole range of refrigerant concen-
tration, in other words the measurement of the refrac-
tive index is useful for both measurements of the
refrigerant concentration in the oil and the oil concen-
tration in the refrigerant. The difference between R134a
and PAG refractive indices is about 0.25 and it corre-
sponds to about 3000 in the resolution of the sensor.
Therefore, the precision of the refrigerant concentration
of 2103 is obtained considering the fluctuation of the
sensor output and the error of the calibration curve.
However, since the accuracy of the sampling method in
this study is not sufficient, more measurements are
needed to get an accurate correlation between the mixing
concentration and the refractive index of the mixture.
The refractive index of the R410A/PVE oil mixture
versus refrigerant concentration is shown in Fig. 10 with
temperature as the parameter. It shows almost the same
tendency as that described for the previous figure. When

Fig. 8. Refractive indices of R600a and Paraffinic oil.

Table 1
Refractive indices of refrigerants and oils

Substance 30  C 40  C 50  C

R134a 1.213 1.206 1.197


R410A 1.186 1.175 1.163
R32 1.191 1.182 1.171
R125 1.181 1.168 1.156
R600a 1.314 1.306 1.297
PAGa 1.453 1.450 1.448
PVEa 1.443 1.441 1.438
Paraffinic oila 1.472 1.466 1.464
a
Refractive indices of oils depend on each oils; additives, Fig. 9. Relationship between refractive index and refrigerant
viscosity grade and molecular structure of the oil. concentration (R134a/PAG oil).
M. Fukuta et al. / International Journal of Refrigeration 27 (2004) 346–352 351

Fig. 10. Relationship between refractive index and refrigerant Fig. 11. Influence of oil degradation on refractive index.
concentration (R410A/PVE oil).

the temperature is higher than 40  C and the refrigerant has no influence on the measurement. On the other
concentration is from 0.7 to 0.9, there is no data in the hand, the existence of bubbles does disturb the
figure. In this region, since R410A and the PVE oil used measurement and the sensor output becomes unstable.
in this study become immiscible, the mixture gets cloudy
like emulsion, and the sensor does not work under such
conditions. 4. Conclusion

3.4. Influence of oil degradation The refractive index of refrigerant/oil mixture was
measured under pressurized conditions. Almost the
Oil degradation and moisture absorption into the oil same output as designed was obtained with a measuring
occur in practical refrigeration cycles and compressors. unit utilizing a laser displacement sensor. The uncer-
The influence of them on the refractive index is investi- tainty of the refractive index sensor was less than
gated for the practical use of the refractive index 5104, and that of the mixing concentration of refrig-
measurement. Fig. 11 shows the refractive indices of erant/oil mixture was less than 2103. For the combin-
PVE oils. The oils used here are PVE oil of VG68 as a ations of R134a/PAG oil, R410A/PVE oil and R600a/
base oil, PVE oil with high moisture contents (500 and mineral oil, the difference of refractive index between
1000 ppm) and degraded PVE oil whose total acid the refrigerant and the oil was large enough to detect the
number (TAN) is 0.25. Note that the vertical axes is so mixing concentration of refrigerant/oil mixture. The
magnified that the difference becomes clear. The refrac- refractive index of refrigerant decreases with increasing
tive indices in case of the 500 ppm moisture and temperature, whereas that of oil is less sensitive to
TAN=0.25 are almost the same as that of the base oil, temperature. Since the refractive index of the refriger-
although the refractive index of the extremely moist oil ant/oil mixture changes almost linearly according to the
of 1000 ppm is slightly higher than the base oil’s. The mixing concentration of refrigerant/oil mixture over
result means that the concentration measurement of the whole concentration range, the measurement of
refrigerant/oil mixture by detecting the refractive index refractive index can be applicable to the measurements
will be applicable to the practical refrigeration cycles of both the refrigerant concentration in the oil and the
and the compressors. In Fig. 11, the refractive index of oil concentration in the refrigerant. In addition, even if a
PVE oil of smaller viscosity grade (VG32) is also shown selective dissolution of R32 and R125 occurs in the
as a reference. It shows smaller value than that of the mixing of R410A with the refrigeration oil and the oil
higher viscosity oil (VG68). degradation occurs, the measurement of refractive index
Furthermore, the influences of flow and bubble exis- is applicable to practical cycles to measure the mixing
tence on the measurement were investigated. Although concentration of refrigerant/oil mixture. In the next
the output is slightly unstable by fluctuation of local phase of this study, we have a plan to investigate the
concentration of refrigerant/oil mixture when the mix- refractive index more precisely in the range where the oil
ture is flowing through the sensor section, the flow itself concentration in the liquid refrigerant is less than 1% by
352 M. Fukuta et al. / International Journal of Refrigeration 27 (2004) 346–352

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