Purdue University
`Purdue e-Pubs
`International Refrigeration and Air Conditioning
`Conference
`
`1992
`
`Characteristics of HFC Refrigerants
`
`School of Mechanical Engineering
`
`S. Uemura
`Daikin Industries Ltd.; Japan
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`S. Inagaki
`Daikin Industries Ltd.; Japan
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`N. Kobayashi
`Daikin Industries Ltd.; Japan
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`T. Teraoka
`Daikin Industries Ltd.; Japan
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`M. Noguchi
`Daikin Industries Ltd.; Japan
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`Follow this and additional works at: http://docs.lib.purdue.edu/iracc
`
`Uemura S.; Inagak S.; Kobayash N.; Teraoka T.; and Noguch M. "Character st cs of HFC Refr gerants" (1992). International
`Refrigeration and Air Conditioning Conference. Paper 177.
`http://docs.l b.purdue.edu/ racc/177
`
`Th s docu e as bee ade ava ab e
`add o a
`o
`a o .
`Co p e e p oceed gs ay be acqu ed
`He
`ck/Eve s/o de
`.
`
`oug Pu due e-Pubs, a se v ce o e Pu due U ve s y L b a es. P ease co ac epubs@pu due.edu o
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` p
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` a d o CD-ROM d ec y o e Ray W. He
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`ck Labo a o es a ttps://e g ee
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`g.pu due.edu/
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`Arkema Exhibit 1014
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`Page 1 of 11
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`CHARACTERISTICS OF HFC REFRIGERANTS
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`Shigehiro Uemura, Sadayasu Inagaki, Noboru Kobayashi and Takuya Teraoka
`Mechanical Engineering Laboratory
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`Masahiro Noguchi
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`Chemical Division
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`DAIKIN Industries, Ltd., 1304 Kanaoka-Cho, Sakai, Osaka, JAPAN
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`ABSTRACT
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`Production restriction of CFC's which are used for refrigerators and air
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`conditioners has been implemented through the international mutual agreement
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`approved by the Montreal Protocol. Due to the less impact on the ozone layer
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`depletion, alternative refrigerants for CFC‘s are R-123, R-22 and R-134a.
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`However, HCFC refrigerants R-123 and R-22 do not completely prevent the
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`ozone layer depletion. This paper presents the investigation results of HFC
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`refrigerants R-125, R-143a, R-152a and R-32 which prevent the ozone layer
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`depletion and are candidates for alternatives of Cl’-"C's and HCFC's.
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`The test results of thermal stability of these refrigerants are similar to
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`those of R-12 and R-22.
`The test results show that each refrigerant has
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`different material compatibility.
`The test results of lubricant solubility show
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`that synthetic oils are soluble in these refrigerants, but
`the mineral oils
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`currently in use for CFC's and I-ICFC's are not. The refrigeration performance
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`based on the calculated thermodynamic properties corresponds with that of the
`experimental results.
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`INTRODUCTION
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`these HFC refrigerants are drawing attention as candidates for
`Recently,
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`alternatives without the ozone layer depletion. However, the data are insufficient
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`for officially adopting them as alternatives.
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`This paper presents the investigation results of thermal stability, material
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`compatibility,
`lubricant solubility, thermodynamic properties and refrigeration
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`effect of these refrigerants.
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`EXPERIMENTAL METHODS AND RESULTS
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`Table 1 shows the thermophysical properties of these new refrigerants
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`R-125, R—143a, R—l52a and R-32 in comparison with conventional refrigerants
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`R-134a, R-12 and R-22 [1-5].
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`Page 2 of 11
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`Page 2 of 11
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`Lubricant solubility
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`We conducted the test with 4 kinds of oil by varying the mixture ratio of
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`oil and refrigerant from 20 to 80wt.% and the temperature of the mixture from
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`-70 to 90 °C. The oils used for the test are polyalkylene glycol (PAG), ester
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`and perfluoro ether (PFE) which were exclusively developed by oil makers for
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`R-134a and the mineral oil currently used for R-12 and R22. Table 2 shows
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`the physical properties of oils.
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`The results of oil solubility test show that the mineral oils currently
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`are not
`soluble in
`these refrigerants within the
`limit of
`in use
`these
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`experimental conditions.
`Figures 1--3 show the results of other lubricants.
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`Only PI-"E is soluble in R-143a. PAG and ester are soluble in R32 and R-152a.
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`All of the tested synthetic oils are soluble in R-125 and R-134a.
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`Therrnal-stability
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`Table 3 shows the test conditions. The ‘oils used for this test are soluble
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`in these refrigerants.
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`Figure 4 shows the test results of thermal stability. According to the
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`analysis of the refrigerant decomposition using an ion chromatography under the
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`30-day heating test, the experimental results show that each tested refrigerant has
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`thermal stability similar to that of R-12 and R-22. However, each refrigerant has
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`different catalysis effect depending on the material.
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`Material compatibility
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`factor
`Material
`for evaluating the
`an important
`compatibility is
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`reliability of refrigerating systems. Therefore, we investigated the material
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`compatibility of polymeric materials such as plastics and elastomers which are
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`commonly used for air-conditioners and refrigerators.
`The evaluation of
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`material compatibility is based on the amount of the refrigerant absorbed by
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`the material during the 2 week test of the material being immersed in the 50°C
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`saturated liquid refrigerant and the amount of the material absorbed by the
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`refrigerant after this test and until
`the refrigerant evaporates out under the
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`atmospheric pressure.
`Table 3
`shows
`the tested material
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`conditions.
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`results.
`Each refrigerant has different
`Figures 5--11 shows the test
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`material compatibility. Epoxy resin has relatively strong solubility in these
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`refrigerants. Therefore, epoxy resin is not desirable for the use with those
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`refrigerants.
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`Page 3 of 11
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`Performance
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`The refrigeration performance based on the thermodynamic properties
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`which are the calculated results using Mark O. McLinden's equation of critical
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`parameters, vapor pressure and the ideal gas specific heat capacity.
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`Figure 11 shows the total system for testing refrigeration performance.
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`A rotary type compressor and double-tube type heat exchangers are used for the
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`test. Lubricants used for the test are PFE for R-143a and PAG for the other
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`refrigerants.
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`results of refrigeration
`theoretical and experimental
`Table 4 shows
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`performance under the same operating conditions. It shows the capacity and COP
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`ratio of R-134a against
`the other refrigerants and the discharge temperature
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`difference between R-134a and the other refrigerants. The refrigerants of lower
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`boiling point such as R-32 gives higher capacity than those of higher boiling
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`point such as R-152a. Figure 12 shows the calculated refrigeration capacity of
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`these refrigerants under various evaporating and condensing temperatures. Due to
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`high suction gas density,
`refrigeration capacity increases
`as evaporating
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`temperature rises.
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`the calculated COP of "R-152a is the highest
`Table 4 shows that
`in
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`comparison with other refrigerants and that of R-125 is
`the lowest. The
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`experimental COPS of R-125, R-143a and R-32 correspond with the calculated
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`COP, but those of R—l52a and R—134a do not correspond. The compressor used
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`for this test is for R-22. Therefore, the experimental COP of R-125 which has
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`similar property of R-22 correspond to the calculated COP. However,
`the
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`property of R-152a is not similar to R-22. Therefore, the experimental COPS of
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`R—l52a and R-134a do not correspond to the calculated COP. If a compressor is
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`designed specifically for these refrigerants,
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`correspond with the experimental one. Figure 13 shows calculation data of COP
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`under various evaporating and condensing temperatures. Under these operating
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`conditions, as evaporating temperature rises, the COP of R-125 decreases and the
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`COP of R-152a increases.
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`The discharge temperature of R-32 is the highest of all and those of
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`R~1S2a, R-143a R-134a and R-125 follow. Therefore, R-32 is not desirable for
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`practical application from the point view of high discharge pressure and
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`temperature.
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`CONCLUSION
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`The preliminary investigation results show that I-IFC refrigerants such as
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`R-125, R-143a, R-152a and R-32 are prospective alternatives for CFC's and
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`HCFC's without ozone layer depletion.
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`Though the mineral oils which are currently in use for CFC's and I-lCFC's
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`cannot be used as lubricant oil for these refrigerants, the tested synthetic oils
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`(such as PAG, PFE and ester oils) are soluble. The thermal stability is similar to
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`those of R-12 and R-22. These refrigerants have good material compatibility with
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`the tested polymeric materials except for epoxy resin. R-152a has the highest
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`COP, but the refrigeration capacity per unit displacement is low. R-32 gives the
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`highest refrigeration capacity per unit displacement, but the discharge pressure
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`and temperature are higher than those of other refrigerants.
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`Therefore, this investigation results at this stage do not conclude which
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`I-IFC refrigerant is the most suitable as an alternative refrigerant. The future
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`investigation includes the safety test to confirm the toxicity and flammability,
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`the test of R-32 mixed with other refrigerants to confirm the possibility of
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`this refrigerant as an alternative,
`the test of these refrigerants for obtaining
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`more details of properties for finalization and the practical
`test
`to confirm
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`the material compatibility and the lubricant issues over a long period.
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`REFERENCE
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`[1] Mark O.McLinden, "Thenrtodynamic properties of CFC alternatives:
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`A Survey of the available data" International Journal of Refrigeration (1990)
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`Vol.13, ppl49-162
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`[2] Proceedings of ASI-IR.AE's 1939 CFC's Technology Conference
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`[3] Montreal Protocol Review Meeting (1990)
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`[4] "The'rrnophysical Properties of Environmentally Acceptable Fluorocarbon,
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`HFC-134a and l-ICFC-123" (1991), Japanese Association of Refrigeration and
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`Japan Flon Gas Association
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`[5] International Joint Research Project on Thermophysical Properties of
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`Alternative Flon, IEA-Annex (Annual Report 1990)
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`[6] H.Yama.moto and S.Uemura “Development of Alternative Fluorocarbon
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`refrigerant" Journal of Japan Society of Mechanical Engineering, 1991,
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`Vol.94, No.869, pp.59-62
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`[7] S.lnagaki, N.Kobayashi, M.Noguchi, T.Teraol<a and S.Uemura,
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`"Comparison of HFC Refrigerants", Proceedings of 1991 JAR Annual
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`Conference, pp.41—44
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`Page 5 of 11
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`3“
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`Page 5 of 11
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`Tab|e.1 Triermophysical properties for HFC refriQ9Tan*3
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`Critical
`-1
`‘
`‘
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`G w P
`o D P
`“;',c;'i':.,'}"ar
`?e'.3$',§§§a.u.e
`Refrigerant
`::i':-:19
`Dressure
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`‘c
`C
`We
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`CHgCi-IF;
`-24.2
`113.3
`4520
`R152 5
`5535
`0
`0-03
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`33”
`73-‘
`-47-7
`CH5 CF3
`H143 a
`54.04
`°
`°'7"'
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`3531
`66.3
`-45.6
`120.02
`CHF2CFa
`R 125
`0
`0-55
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`R 32
`73.4
`5530
`CH2 F2
`52.02
`-51.0
`0
`0'13
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`Q25
`R134 3
`CH2FCF3
`102.03
`-25.2
`101-15
`4065
`°
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`3-°
`R 12
`‘-0
`car; 1:2
`120.91
`-29.0
`111.80
`4125
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`CHCIF2
`86.47
`0.05
`0-34
`Fl 22
`-40.3
`95.15
`4903
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`Tabie.2 Physical properties of oils
`1%
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`1H
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`E P
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`A G : Polyalkylene glycol
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`P F E : Perfiuoro ether
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`100
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`R32 H125 F‘i143a Fi134a Fi‘i52a
`
`
`
`
`
`
`
`
`
`
`
`
`Fig.1 Lubricant solubility (P A G)
`
`
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`Page 6 of 11
`
`389
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`
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`03O
`
`G)0
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`Temperature('0) 83
`
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`
`
`Separation
`H
`
`Page 6 of 11
`
`

`
`1 00
`BO
`
`60
`
`40
`
`20
`
`
`
`Temperature
`
`
`
`
`
`(‘(3)
`
`C)
`
`
`
`Temperature
`
`
`
`
`
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`
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`
`
`
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`
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`
`
`-20
`
`-40
`
`-60
`-60
`
`100
`
`-I:0
`
`
`
`
`
`
`
`Separation
`Separation
`
`
`
`
`
`
`
`
`
`
`
`
`Separation
`
`
`
`
`
`
`
`H32 H125 R1434; Fl134a Fl152a
`
`
`
`Fig.2 Lubricant solubility (P F E)
`
`
`
`
`
`
`
`
`
`
`
`5E 2 5
`
`
`
`
`
`
`H32 H125 H1433 Fi134a H1523
`
`
`
`
`
`Fig.3 Lubricant solubility (Ester oil)
`
`
`
`
`
`
`-3
`
`.
`
`
`
`
`
`
`
`M‘
`
`
`
`'1
`
`
`
`l
`
`
`
`
`
`
`
`
`
`
`
`Table.3 Condition of thermal stability test
`
`
`
`
`
`
`
`
`R32
`Fi152a R143a R22
`R125
`
`
`
`
`
`P As .ester on
`(Napl1Theer:e:"eries)
`
`
`
`
`
`
`
`0 W
`
`
`
`
`
`
`
`
`
`
`0.0 , 0.2%-
`
`ater
`
`
`_
`
`T.
`
`
`Rg§'V%f°;f')“
`
`Lubrication oil
`(gm)
`
`
`
`
`
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`
`
`
`
`
`
`
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`Page 7 of 11
`
`390
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`Page 7 of 11
`
`

`
`ZK—
`
`
`
`:
`:1 Fa
`
`Al
`
`
`02¢/3 uzuzlarllt
`jCu
`
`
`
`
`
`
`
`
`
`
`
` 0‘2°/°
`
`
`PAG
`
`0.2%
`
`
`
`
`
`
`PFE
`
`
`
`
`
`
`
`
`
`0.2%
`
`
`02°62 '"
`Eli
`
`0.2%H
`ti
`liisig
`''' lllJ
`
`
`
`
`
`0.2°/
`
`
`
`- --
`
`Ester oil
`
`
`
`'
`
`
`
`10"
`_
`1 0'
`1 0°
`
`
`
`
`
`
`Quantity of generated F-ion (ppm)
`
`
`
`
`
`Fig.4 F-lesult of thermal stability test
`
`
`
`
`
`
`
`l 0
`
`
`
`
`
`
`
`
`
`
`Table.4 Condition of material compatibility test
`
`
`
`Rubbers
`
`
`Nitrile rubber
`
`
`Silicon rubber
`
`
`Fluorocarbon rubber
`
`
`Acrylic rubber
`
`
`Chloroprene rubber
`
`
`
`Epoxide resin
`
`
`P I
`t
`f'b
`
`
`er
`Dyes er
`Polyester film
`
`
`Tetron fiber
`
`
`
`
` Heating period
`
`
`
`
`
`Plastics
`
`
`
`
`
`
` Temperature
`
`
`
`Material
`
`
`Page 8 of 11
`
`391
`
`
`
`Ester oilIIIlllllllEl
`
`
`
`
`
`0'29/U T
`
`
`PAG
`
`0.2%
`
`
`
`
`
`
`
`
`
`
`
`
`Page 8 of 11
`
`

`
`
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`
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`
`
`
`1‘'.
`umgmu,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Fig.5 Result of material compatibility ‘te5t(Fi32)
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Fluorocarbon
`rubber
`
`Chloroprene
`b
`
`Epoxude resin
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
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`
`
`
`
`
`
`
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`
`
`
`
`
`
`
`
`
`
`
`
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`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Tetron fiber
`
`
`
`
`
`Nitrile rubber
`
`
`Silicon mbber
`
`
`Fluorocarb-o-rt.-'-
`
`
`
`
`Chloropren-e
`
`...r.'=I.|.>.b.e.r.._...
`
`
`
`Epoxide resin
`
`
`1 r fiber
`
`Polyester iilrn
`
`Poly
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
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`
`
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`
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`
`
`
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`
`
`
`
`
`
`
`
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`
`
`
`
`
`
`
`
`
`
`—5‘o
`
`
`o
`
`
`
`5-0
`
`
`
`
`1l'3o_l'5o 20006)
`
`
`
`
`
`
`
`
`
`D Swelling
`-Extraction’
`
`
`
`
`
`
`
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`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Polyester llber
`
`Polyester film
`
`
`
`
`
`
`
`
`
`
`
`
`Elswelling
`-
`
`
`
`
`Fig.6 Result of material compatibility test (R125).Exiraciion
`
`
`
`
`Tetron fiber
`Tetron liber
`
`Nitrile rubber
`
`
`Silicon rubber
`
`
`"6i{i&?5§'re e
`
`..ml?h§!..............
`
`E oxide resin
`
`
`
`
`
`
`
`
`’
`
`
`Polyester fiber
`
`
`Polyester film
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
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`.
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`
`
`Difiweiling
`
`
`
`
`Fig.7 Result of material compatibility test(R143a) _Extraclion
`
`
`
`
`
`
`
`
`
`Page 9 of 11
`
`392
`
`
`
`Page 9 of 11
`
`

`
`Nitrile rubber
`
`
`
`
`
`
`
`
`
`Fluorocarbon
`rubber
`
`
`
`
`
`
`
`
`Polyester fiber
`
`
`Polyester lilm
`
`
`
`
`Telron llber
`
`2 0 0
`
`
`|:| Swelling
`
`
`
`Fig.8 Result of material compatibility test (Fl152a) .Exlrar.-lion
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
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`
`
`
`
`
`
`(96)
`
`,
`
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`
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`
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`
`
`
`
`
`
`Fluorccarbon
`rubber
`
`lic rubber
`
`Epoxld§ resin
`
`
`
`
`
`
`
`
`
`Polyester liber
`
`Polyester lilm
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Telron fiber
`Tetron liber
`
`
`...........
`
`
`
`
`
`
`
`
`
`
`
`
`..............}.............;..........
`
`
`5
`
`
`
`
`
`
`
`
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`
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`
`
`
`
`
`
`
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`Polyester lilrn
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
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`
`
`
`
`
`
`
`2 63 (95)
`
`
`
`El Swelling
`
`
`
`
`
`
`Fig.10 Result of material compatibility test (H22) 'Exlraclion
`
`
`
`Page 10 of 11
`
`393
`
`
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`
`
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`
`
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`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Nilrile rubber
`............
`Silicon rubber
`
`
`Fluorocarbcn
`
`rubber
`
`
`Acrylic rubber
`
`
`........................
`
`rubber
`Chloroprene
`
`Epoxide resin
`
`
`
`
`Polyester fiber
`
`
`
`
`
`
`‘
`
`
`
`
`
`
`
`'
`_
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`:
`
`
`
`
`
`3
`
`
`
`
`
`
`
`
`
`
`
`
`
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`
`
`
`
`
`
`
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`
`
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`
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`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`I_—_|Swelling
`
`
`
`
`
`
`Fig.9 Result of material compatibility test(Fl12) -Extraction
`
`
`Page 10 of 11
`
`

`
`
`
`Conlvl valve
`
`Hen Iink Hui!
`
`® Turrperuur: uuaor
`
`
`_® Prunrre sensor
`
`
`(2) Flour «mar
`
`
`
`
`
`
`
`® Elude page new
`
`
`
`Fig.11 Total system for testing refrigeration performance
`
`
`
`
`
`
`
`
`Table.5 Performance for HFC refrigerants
`
`
`
`
`
`
`Evaporating Condensing a'5°"a’93
`
`
`
`pressure
`pressure
`di'rP:rée§:‘a.:"e"e
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`, 0
`as
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Calculated
`
`
`
`
`
`
`
`
`
`
`
`Ee
`
`
`
`H1433
`
`
`
`
`
`H32
`
`
`
`
`
`
`m 0.728
`2.06
`
`
`
`
`
`
`mulated ED -
`
`
`
`
`3%
`
`
`
`0. 49
`carcuiateu EE 9
`
`
`
`
`£15
`
`
`
`
`
`-I-Operating conditrons:Evaporating temp. 5'C. Condensing temp. 45‘C.
`
`
`
`
`
`Suparheai 9'C. Subcool
`t0'C
`
`
`
`
`
`
`
`
`-It-Capacrtyzcooling capacity per suction volume oi compressor
`
`
`
`
`
`
`
`
`5°M.,,,i,,g “ml _ E,,.m,“,,g lam“ , wt
`
`
`
`
`
`
`
`
`
`
`‘%
`" 0.9
`
`ca.
`
`8
`0.5
`
` 1.0
`
`.9
`*5
`.3‘
`§
`%
`0
`
`910
`
`
`
`
`2°
`
`
`10
`0
`
`
`Evaporating temperature ('C)
`
`
`
`Fig.12 Characteristics of cooling capacity
`
`
`
`
`
`
`
`
`
`
`
`
`Condensing temp. . Evaporulmg mnp. . 401?.
`
`
`
`
`
`
`
`
`
`
`‘S23
`
`
`
`
`
`
`
`20
`
`
`10
`o
`
`
`
`EVBPDWUHQ temperature ('C)
`
`
`
`
`Fig.13 COP characteristics
`
`
`
`
`
`0.7
`-10 '
`
`
`
`
`Page 11 of 11
`
`39:.
`
`
`
`Page 11 of 11