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International Compressor Engineering Conference

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Practical Stability Performance of Polyvinylether
(PVE) With HFC Refrigerants
S. Tominaga
Idemitsu Kosan Co.

M. Takagi
Idemitsu Kosan Co.

M. Takesue
Idemitsu Kosan Co.

T. Tazaki
Idemitsu Kosan Co.

M. Goodin
Apollo America Corporation

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Tominaga, S.; Takagi, M.; Takesue, M.; Tazaki, T.; and Goodin, M., "Practical Stability Performance of Polyvinylether (PVE) With
HFC Refrigerants" (2000). International Compressor Engineering Conference. Paper 1386.

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Minoru Takagi Lubricants Department. non-hydrolysis nature Ol. autoclave tests with water and air were performed to determine the reliability limit of PVE in comparison with mineral oil and polyolester. INTRODUCTION PVE was introduced as an innovative refrigeration oil for HFC refrigerant systems. oil film strength in EHD region (3). Furthermore. Idemitsu Kosan Co. Idemitsu Kosan Co. IN.. it was confirmed that PVE with HFC refrigerant has enough tolerance to air or water contamination to secure long term reliability. effectiveness of anti wear additive <4l and miscibility with HFC refrigerant< 5l were the key characteristics looked at by OEMs who chose PVE_ These performances directly or indirectly contribute to the total cost down of systems_ For example. The characteristics of PVE were reported many times in the past. Ltd_ Mark Goodin Apollo America Corporation. Among these. deterioration of PVE itself was not observed and long term reliability was confirmed. Tokyo Japan (E-mail: 49002320@si. Toshinori Tazaki Lubricants Research and Development Laboratory. Southfield. In this report. solubility with process fluid (2). most ofPVE users do not use filter dryers for HFC air conditioners by controlling equilibrium water in systems less than a few hundred ppm <6 l_ By confirming these advantages through numerous actual machine tests.. we gathered the used oil analysis data after the above mentioned machine tests to determine the practical stability performance of PVE.jp) Masahiko Takesue.idemitsu.co.com) ABSTRACT Deterioration degree of PVE Lubricants was investigated by analyzing used oils after various compressor and system tests with HFC refrigerants_ As a result. MI (E-mail: mgoodin@apolloamerica. USA. 2000 201 . Through these studies. OEMs worldwide have begun to use PVE for commercial product applications. Ltd. West Lafayette. Fifteenth International Compressor Engineering Conference at Purdue University.PRACTICAL STABILITY PERFORMANCE OF POLYVINYLETHER (PVE) WITH HFC REFRIGERANTS Shoichi Tominaga.July 25-28.

The PVE results were compared to the results ofM056 and POE68. Some of them used R404A for commercial refrigeration application. The compressor types were mainly rotary and scroll. AI) Pressure Bomb Oil & Refrigerant Factors Air Catalyst (Fe.96 12 7.E+14 8. 1 Autoclave Test Fifteenth International Compressor Engineering Conference at Purdue University. Others were performed with water or air premising insufficient air or water removal when these systems would be installed or repaired.926 0. USA. Reliability limits of PVE68 were evaluated by autoclave testing under more severe conditions.E+I4 8. Figure 1 shows autoclave testing apparatus Table 2 Autoclave Test Conditions (Duration: 30days at 175 °C. The lubricant samples analyzed were taken from either in the middle of the test or after the test.960 0.67 77 5. 2000 Test Conlitions lOtorr> 200torr 760torr 50 ppm> 500ppm l. a total of 183 samples were analyzed. Some of these tests were performed with contaminants such as rust preventive oil or cutting oil premising insufficient washing process of compressor parts.01> 0.E+13 Antioxidant Antioxidant Antioxidant Antiwear Antiwear Antiwear Acid catcher Acid catcher each oil. The test conditions varied from normal operating conditions to accelerated life test conditions.TEST METHOD AND CONDITIONS Because of the many number of Table 1 General Specification ofEach Oil samples. In addition to this oil.July 25-28.68 88 0.2 54. West Lafayette.918 -40 -35 -35 0. PVE VG 68 (PVE68) with antioxidant.2 7.9 60. Catalyst :Fe. IN. Table 1 shows the general specifications for Additives M056 POE68 64. naphthenic mineral oil VG56 (M056) and fully branched polyolester VG68 (POE68) Viscosity Index 3 Demity (g/cm @ I5°C) (oC) Pour Point Total Acid Number(IJW(OHII() Volumelri: Resistivity (Q ·em.01 l. Most of refrigerants used in these tests were either R407C or R410A. acid catcher and antiwear PVE68 V~cosity 2 (nnn /s @ 40°C} 2 (nnn /s @I00°C) additive was chosen as the candidate oil to be analyzed.OOOppm Significance Prnctical operation Air contamination Abnormal rondition Prnctical operation Water contamination Abnormal rondition 202 .Al) Water Fig.01> 0. OEM's have created accelerated life test conditions depending upon scope and purpose.Cu. Cu. with many not using filter dryers. Among the numerous durability tests conducted with PVE 68 by using actual compressors and systems. RT) were used in autoclave testing as a reference.

.00 ~~~: --~-[E··~-~-.16 ~ :f: e..... In these studies..000 4.1 ~ Oil <:: ·a ·..1 E 0 8..08 E 0 -~ 60 1 .. A few samples operated in systems for more than 4.. IN.. Among these data.000 4o r . Most of the samples showed more than 80 % of remaining ratio. it was concluded that no Fifteenth International Compressor Engineering Conference at Purdue University... which is considered sufficient enough to ensure long term effectiveness of anti wear performance at a rubbing surface.000 6... USA. Figure 3 shows the consumption ratio for a phosphorous type antiwear additive..... 2 TAN after Endurance Tests 20 1 ..l 2. Duration(hrs) Fig.20 0 0 0._. 100 0.000 ... TEST RESULTS AND ANALYSIS Endurance Test Results Figure 2 shows the relationship between test duration and Total Acid Number (TAN) for 183 samples.....04 0.. the relationship between test duration and consumption of each additive were studied.... R410A refrigerant was used for PVE68 I POE68 and R22 refrigerant was used for M056 testing.. ~ ~ ::r:: ~00 0.July 25-28. sulfur..000 12...000 6.. some showed significant TAN increases in a relatively short period of the test time and chlorine.. Even after long term operation.000 hours or more.. Since TAN increase was not observed.:~:-::. the overall TAN increase is minimal for PVE68 and considered having superior stability in an actual machine.. 00 G) ~ @@ 0... Since these substances are not contained in the original oil and well known as additives used in rust preventive or cutting oils.~-~~-jfm~·::_ . 2000 203 ...___j _3''b... ~:?!-=~·Q!·-. 3 Antiwear Additive Contents after Endurance Tests Next we studied the consumption ratio of antioxidant which results were plotted on Figure 4...12 ~ E- 0. we studied the relationship between the antioxidant consumption ratio and TAN increases for the samples that operated for a duration of 4.000 hours showed much lower remaining ratios...000 0 L---~----~--~----~--~~--~ 0 12. Figure 5 shows the results.and Table 2 shows the test conditions.L:-_OQ_:- Q!· 0 2. In order to investigate precisely the stability performance of PVE68.. Therefore.000 Duration(hrs) Fig...000 8. West Lafayette..000 10.000 4. it was determined that these lubricant samples came from test systems that experienced insufficient washing processes or contaminants were intentionally added to make the test condition more severe.. potassium or barium were detected.000 I 0. Most of the samples showed more than 60 %remaining ratio.

Therefore. autoclave test were performed to confirm the reliability limit ofPVE68 under more severe conditions. It also reacts with water and reduces the water content in systems. 40 0. In order to clarify the effect of air and water contamination.--. Naphthenic mineral oil which has been used as a refrigeration oil for R22 and polyolester which is used with HFC refrigerant were also evaluated as a reference.12 ~ !0. USA. it reacts with these substances and is consumed rapidly.000 4..000 12.July 25-28.000 10. 4 Antioxidant Contents after Endurance Tests lb @ w 00 ~ ~ 0S ~ @ 100 Remaining Ratio(%) Fig. 2000 204 .000 8.000 Duration(hrs) Fig. when amount of water or contaminants are high.000 0. Sometimes it was consumed relatively early and other times it remained sufficiently after a long duration. IN. the test conditions listed on Table 2 were Fifteenth International Compressor Engineering Conference at Purdue University.000 8. there is no clear relation between duration and residual contents. 5 Remaining Antioxidant and TAN deterioration ofPVE base oil occurred even for the samples that showed lower antioxidant ratios. additives or refrigeration oil itself.04 Ill lb 0 L---~----~--~----~--~--~ 0 2. acidic substances and water in the oil and prevented the base oil from deterioration.000 6.000 10.00 0 Duration(hrs) Fig.08 <I> ~ 20 0. The purpose of this additive is to neutralize the acidic substances which are introduced into the system by contaminants or generated by deterioration of contaminants.000 6. Unlike other additives. We assume the cause of this data fluctuation is that the acid catcher reacted with water or contaminants in the system in relatively early stage of the operation and reacted with deteriorated substances later. 6 Acid Catcher Contents after Endurance Tests Autoclave Test Since deterioration of PVE68 was not observed through endurance tests.16 0 0 -~ 00 5:: 60 0 ~ 00 ·ac ·a s ~ &. Figure 6 shows the same kind of relationship for the acid catcher. 0 2.. In this way..000 12.000 4. West Lafayette. ~ 100 020 80 0. the additives in PVE68 reacted effectively with oxygen. Furthermore.

Cu. very severe conditions in practical operation and abnormal operating conditions. 500 ppm and 1. In general. It has previously been reported many times that Polyolester will hydrolyze under certain conditions and Polyvinylether will not hydrolyze because of its ether structure<7 l_ This can be reconfirmed throu"gh this study.000 ppm of water was assumed to be caused by hydrolysis of • 7 60 torr 0 200 torr 0 l 0 torr> 0. None of the oils showed TAN increase at less than 50 ppm. Water contents in sample oils were controlled at less than 50 ppm. Again. West Lafayette. Although. In these studies. 2000 0 0.5 TAN(mgKOH/ g) Fig. Next. These tests represent a normal operating condition. vacuum ratio was less than 10 torr and considered no air in the autoclave.000 ppm for all three oils. 760 torr vacuum ratio means no refrigerants but only air and oil in the autoclave. 7 Effect of Air Contamination (175°C. No Water. Catalyst:Fe. AI) 205 .000 ppm content of water. Catalyst:F e.0 02 OA 0~ 0~ LO TAN(mgKOH/g) Fig. test conditions were fixed at 175 °C for 30 days. IN. This is assumed to be because a certain amount of water in air reacted with POE and caused hydrolysis. USA.5 3 3. test conditions were fixed at 175 °C for 30 days and water was controlled at less than 50 ppm. 8 Effect of Water Contamination (175°C. No Air. At this point. All oils showed significant TAN increase at 760 torr. POE has better anti-oxidation performance than PVE or mineral oil. it is confirmed that PVE68 has enough tolerance to a practical amount of air contamination and no worse than a mineral oil/R22 combination. 30 days. however the test results showed otherwise especially when the vacuum ratio was 7 60 torr.5 l LS 2 2. Figure 7 shows the effect of air contamination. POE68 alone showed significant TAN increase at 500 and 1.chosen. while TAN increase was relatively small at less than 50 torr and 200 torr for all three oils and considered to be in an acceptable range. 30 days. Air was removed by vacuum pump at room temperature for 5 minutes. The TAN increase for PVE68 at 1.July 25-28. air contamination is considered to cause oxidation of oil over long term operation. AI) Fifteenth International Compressor Engineering Conference at Purdue University. Cu. Figure 8 shows the test results. the effect of water contamination was studied by carrying out the autoclave tests with different water contents. Air was added in the autoclave by controlling vacuum ratio at 200 and 760 torr respectively.

.antiwear additive. S. Proceedings of Int. M. WA. T. According to these results.. Y. This may be caused by fluctuation of amount of initial water and contaminants in systems.. K. USA. it was confirmed that these samples did not show TAN increase and no deterioration of base oil. 1999 (2)(4)(7) Kawaguchi. Sato. K. M. • The remaining ratio of the acid catcher varied. M. Tominaga. • The autoclave test results suggest that PVE with HFC refrigerant has enough tolerance to air or water contamination even compared to a conventional mineral oil/R22 combination.. S. Nishikawa. CONCLUSION • Numerous PVE oil samples after endurance tests were analyzed. M.July 25-28. • Although a few samples showed low antioxidant remaining ratio after long duration. Takagi. Conference Center Kobe. REFERENCES (1)(5) Kaneko. Tominaga. Matsumoto. it was concluded that PVE68 has sufficient stability with water at least in a practical usage range. 2000 206 . T.. • Enough antiwear additives in PVE remained even after long duration.. IN. Conference Center Kobe.. S.. ARTI MCLR Project No.. 670-54400 Aprill999 (6) Fujikawa. Goodin. Proceedings of Int. ASHRAE Seattle. November 1998 p-78 (3) Gunsel. West Lafayette... November 1998 p-145 Fifteenth International Compressor Engineering Conference at Purdue University. Most of them showed minimal TAN increase and considered to be sufficient to guarantee long term reliability. Pozebanchuk.