IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
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`Mail Stop: Inter Partes Reexam
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`Attn: Central Reexamination Unit
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`Examiner: Ling Xu
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`) ) ) ) ) )
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`In re Reexam Control No. 95/001,783
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`Filed: November 08, 2011
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`U.S. Patent No. 8,033,120 to Singh et al.
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`Title: Compositions and Methods Containing
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`Fluorine Substituted Olefins
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`Art Unit: 3991
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`DECLARATION OF RAYMOND THOMAS
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`BACKGROUND
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`1.
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`My name is Raymond H. Thomas.
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`I am a named inventor on
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`approximately 37 issued U.S. Patents. I am an inventor on U.S. Patent No. 8,033,120
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`(the ‘ 120 patent), I am currently employed by the Patent Owner of the ‘ 120 patent,
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`Honeywell International Inc.
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`2.
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`My educational background includes: Hanover College BA 1970
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`(Chemistry); Miami University MS 1972 (Physical Chemistry); Texas A&M University
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`Ph.D. 1978 (Physical Chemistry); and State University of NY at Buffalo 1994 (MBA).
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`3.
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`My post—university work experience includes Post Doctoral Fellowship at
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`Bartlesville Energy Technology Center (1978-1980).
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`4.
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`Ibegan working at Honeywell International in about 1980 as a Senior
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`Chemist. My current position at Honeywell International is Senior Principal Scientist.
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`5.
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`I consider myself a person skilled in the art of heat transfer compositions
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`based on fluorine containing compounds, such as those claimed in the ‘ 120 patent, and in
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`particular the use of lubricants in such compositions.
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`6.
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`I am familiar with the subject matter of the ‘ 120 patent, and that a request
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`for reexamination has been filed with respect to that patent.
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`I have reviewed and
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`PH1 3294297v3 10/15/12
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`— Page 1 —
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`Page 1 of 23
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`Arkema Exhibit 1057
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`Arkema Exhibit 1057
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`understand the claims being filed in connection with the response to the Action Closing
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`Prosecution action in the above—identified matter (hereinafter “the Response”).
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`7.
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`I have reviewed and am familiar with the information contained in the
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`English translation of JP041 10388 — Inagaki (hereinafter “Inagaki”) that I understand was
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`previously submitted to the Patent Office in the reexamination proceedings of the ‘ 120
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`patent. I am aware that Inagaki contains a process flow diagram (Figure 2) which shows
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`the presence of an “oil separator” located downstream of the compressor in the system
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`contemplated for use by Inagaki.
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`8.
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`Based on my knowledge, experience and expertise, it would not be the
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`normal case to include an oil separator in a heat transfer system when such a system was
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`expected to use a heat transfer compound in combination with a lubricant with which it
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`had acceptable miscibility and/or solubility. The main reason to include an oil separator
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`in a heat transfer system is to accommodate the use in the system of a heat transfer
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`compound in combination with a lubricant with which it does not have acceptable
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`miscibility.
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`9.
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`Using an oil separator or specifying an oil separator for use in a heat
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`transfer system has the disadvantage of increasing the cost and complexity of the system.
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`An oil separator will also generally require that the system will occupy more space,
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`which in many systems is also a disadvantage.
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`10.
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`There are a few, relatively rare, circumstances in which an oil separator
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`might be included in a heat transfer system even if there is sufficient miscibility and/or
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`solubility between the refrigerant and the lubricant. One such situation might exist when
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`the particulars of the piping design call for extraordinarily long piping between a
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`compressor and a condenser. Another example may be in the case where the system uses
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`certain flooded evaporators. Inagaki does not describe any special circumstance that
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`might require an oil separator even if there were sufficient miscibility and/or solubility
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`between the refrigerant and the lubricant.
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`ll.
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`I am familiar with the specification of the ‘ 120 Patent, including the
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`Examples thereof. With respect to Example 2 of the ‘ 120 Patent, that example describes
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`testing to determine the miscibility of certain molecules with certain lubricants under
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`certain conditions, and a person skilled in the art reading Example 2 would understand it
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`to be a miscibility test.
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`12. Within the time period from about 2007 to the present, Ihave supervised
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`and/or conducted several instances of supplemental testing on refrigerant/lubricant pairs
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`using the same or similar techniques to those disclosed in Example 2. The supplemental
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`testing has included testing on three different classes of lubricants. The first class of
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`lubricant, which is a widely used lubricant in the refrigeration industry, is mineral oil.
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`The mineral oil which was the subject of supplemental testing and which is the subject of
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`this declaration is representative of mineral oils commonly used in the refrigeration
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`industry and is sold under the trade name C—3S by Nu—Calgon. The second class of
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`lubricant which was the subject of supplemental testing and which is the subject of this
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`declaration is a polyol ester oil (POE) representative of this class of lubricants and is sold
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`under the trade name RL 32—3MAF by CPI . The third class of lubricant which was the
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`subject of supplemental testing and which is the subject of this declaration is a
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`polyalkylene glycol (PAG) representative of this class of lubricants and is sold under the
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`trade name ND—8 by Idemitsu Kosan.
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`13.
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`The supplemental testing Irefer to herein was conducted as part of efforts
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`that included evaluating the miscibility of mixtures consisting of each of the above—noted
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`lubricants and each of trans HFO—l234ze (t—HFO—l234ze) and HFO—l234yf. As a result
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`of these various instances of supplemental testing, I am able to report on the miscibility
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`of these pairs at lubricant:HFO weight ratios of 5:95, 20:80 and 50:50. Moreover, these
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`various instances of supplemental testing have enabled me to report on miscibility for
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`each of these pairs at each of the following temperatures: 0°C, 10°C, 20°C, 30 °C, 40 °C
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`and 50 °C, This supplemental testing included placing mixtures having the above—noted
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`lubricant:HFO ratios, or ratios from which results at the above—noted ratios can be
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`reliably estimated,
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`in a heavy—walled glass tube. The tubes were evacuated, the
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`lubricant/HFO compositions were added, and the tubes were sealed. The tubes were then
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`put into an air bath environmental chamber, the temperature of which is controlled and
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`which included each of the test temperatures mentioned above or at temperatures from
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`which results at the above—noted ratios can be reliably estimated. Visual observations of
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`the tube contents were made after reaching temperature equilibrium for each of the test
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`temperatures. The existence or non—existence of one or more liquid phases is reported by
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`visual observation. In a case where more than one liquid phase is observed, the mixture
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`is reported to be immiscible. In a case where there is only one liquid phase observed, the
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`mixture is reported to be miscible.
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`14.
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`As a result of the supplemental testing described above, I can provide the
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`information reported in Table l which is attached hereto as Exhibit D.
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`The above—noted results were obtained as a result of testing done by
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`Honeywell in its research labs in Buffalo, New York, United States of America at various
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`times from about 2007 up to the present.
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`16.
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`In the tests in Example 2 of the ‘l20 Patent, the percentages of lubricants
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`tested were 5 wt%, 20 wt% and 50 wt%. In order to understand the relevance of these
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`concentrations, it is necessary to understand that for most lubricant/refrigerant pairs one
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`of two types of characteristic miscibility curves will be found. For example, the
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`characteristic miscibility curve for the HFO— l234yf/PAG is attached hereto as Exhibit
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`Thomas C. The attached chart is representative of the type of a curve that is sometimes
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`referred to as a “U—shaped” curve. This type of chart is generally created by first
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`performing test work of the type described above and in Example 2, and for each
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`concentration tested placing a point at the temperature on the graph where two phases are
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`seen to begin to form. This process is repeated for all tested points. A line can be drawn
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`by those skilled in the art based on these points, and such a line provides an
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`approximation of what is known as the miscibility curve. According to such a miscibility
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`curve, the area below the line corresponds to the existence of a single liquid phase, and
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`the line is an approximation of the temperature for any particular concentration at which
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`some level of immiscibility begins to appear. The area above the line is where
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`immiscibility exists.
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`17.
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`The other type of characteristic miscibility curve is illustrated in Exhibit
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`Thomas B, which is the miscibility curve for the HFO—l234yf/Mineral Oil (C3). This
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`curve is generated in the same manner as indicated above, however, the nature of the
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`refrigerant/lubricant pair results in a curve having a different shape, namely one which is
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`sometimes referred to as a Dome—shaped curve. In this particular case, the top of the
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`dome is not shown because the results at the concentrations already plotted were a good
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`indication that no miscibility would be found at any temperature that would be
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`considered useful for heat transfer applications. For this type of curve, the area outside
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`the curve corresponds to the existence of a single liquid phase, and the line again
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`represents an approximation of the temperature for any particular concentration at which
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`some level of immiscibility begins to appear. The area inside the curve represents the
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`region where immiscibility exists.
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`18.
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`In general, my initial testing on miscibility of refrigerant/lubricant pairs
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`uses the three concentrations mentioned herein for several reasons. First, in my
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`experience with these types of refrigerant/lubricant pairs, what is known as the lower
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`critical solution temperature, or LCST, will frequently be found in the general region of
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`about 20% by weight of lubricant concentration for U—shaped miscibility curves. The
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`LCST for such U— shaped miscibility curves represents the temperature below which
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`miscibility exists for all lubricant concentrations, and therefore testing is commonly done
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`at 20% to be in the general region that the LCST is frequently found. Testing is often
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`done at 50% by weight of lubricant because it is sufficiently removed from the 20%
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`concentration to provide meaningful information about the specific shape of the curve.
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`Similarly, testing is frequently done at about 5% by weight of lubricant because it is
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`sufficiently removed from the 20% concentration on the low side to also provide
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`meaningful information about the specific shape of the curve.
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`19.
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`In addition to understanding the basic information provided by miscibility
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`testing, including the information provided by the miscibility curves, it is also necessary
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`to explain the operation of a typical vapor compression heat transfer cycle. The amount
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`of lubricant charged to a refrigeration system (hereinafter sometimes referred to as
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`“initial charge”) is usually selected by the original equipment manufacturer (OEM) of the
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`system and can be as high as about 50% by weight based on the total weight of
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`refrigerant and lubricant.
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`In normal operation only a relatively small amount of the
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`lubricant charged into a system will leave the compressor during operation and be carried
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`by the refrigerant vapor discharged from the compressor. The lubricant concentration at
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`the compressor discharge is meaningful because it represents the lubricant which is
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`expected to return to the compressor and therefore is the basis for determining what is
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`known as the oil circulation rate, or the OCR. System efficiency and reliability,
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`including proper functioning of the compressor, require that this amount of lubricant
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`carry—over, or OCR, is returned to the compressor to perform its intended lubricating
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`function, and does not become lodged in the coils and/or other parts of the system.
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`20. While the amount of lubricant carried over from the compressor discharge
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`will vary from system to system, it is typically considered to be fairly represented by the
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`range of from about 3% to about 8% by weight based on the circulating lubricant and
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`refrigerant. However, for the purpose of evaluating use of the lubricant in combination
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`with the refrigerant, it must be understood that circulating weight percent of lubricant
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`(based on the combination of lubricant and refrigerant) can increase somewhat in certain
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`cases. It should be noted that certain refrigerant/lubricant pairs may form a miscibility
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`curve that is different from and more complex than either U— shaped or Dome— shaped
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`curves mentioned above.
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`21.
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`In order to ensure that carry—over lubricant is returned to the compressor,
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`three properties related to the lubricant/refrigerant will usually be considered. The first
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`property is the miscibility of the lubricant with the refrigerant, which for a given
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`concentration is a function of temperature. The second property is the solubility of the
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`refrigerant in the lubricant for those conditions in which immiscibility might exist.
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`Solubility is a relevant factor in large part because of its influence on the third factor,
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`which is viscosity. In general, the viscosity of a liquid phase containing both refrigerant
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`and lubricant will tend to decrease with greater levels of refrigerant solubility in that
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`phase and with increasing temperature. As a result, the relatively lubricant—rich phase in a
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`two—phase system will generally become more flowable as the amount of refrigerant
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`dissolved in that phase increases.
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`The miscibility impacts the ability of the lubricant
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`and the refrigerant to exist as a single liquid phase and therefore move together through
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`the heat transfer system without separation. The viscosity impacts the ability of the
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`lubricant to flow and move through the system if and when it forms a second liquid phase
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`richer in lubricant.
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`22.
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`Different portions of the vapor compression system experience different
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`temperatures. If the lubricant and the refrigerant are fully miscible at all temperatures
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`existing in the system, then there would usually be no concern regarding return of the
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`lubricant to the compressor because all of the lubricant would generally return to the
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`compressor with the refrigerant. Such a condition essentially eliminates in the vast
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`majority of cases the potential for lubricant to accumulate in the system without returning
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`to the compressor. In making this assessment for refrigerant/lubricant pairs having a U-
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`shaped miscibility curve, the LCST of the miscibility curve will be compared to the
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`temperature range in the evaporator since this is generally the lowest temperature in the
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`system. Generally speaking, if the LCST is about the same as or above about the
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`expected temperature in the evaporator, then this provides a good indication that the
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`lubricant/refrigerant pair will be useful in the refrigeration system without the need for an
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`oil separator.
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`23.
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`Miscibility over less than the full temperature range existing in the
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`refrigeration system may be acceptable if the lubricant and refrigerant are sufficiently
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`miscible at the temperatures which typically would exist at the outlet of the expansion
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`valve and in the evaporator. Lubricant that exists in a separate phase under evaporator
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`conditions might tend to accumulate in these portions of the system and not return to the
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`compressor. However, if there is sufficient solubility of the refrigerant in the lubricant at
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`these temperatures to lower the viscosity enough to be flowable, the pair may
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`nevertheless be acceptable for use in a system without an oil separator. In many
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`important commercial applications, the temperatures at the outlet of the expansion valve
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`and in the evaporator typically fall in the range of just below 0°C to around 15°C. As a
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`result, it is meaningful that the lubricant when combined with the refrigerant exhibits
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`miscibility and/or solubility at the temperatures in this range and at lubricant
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`concentrations of from about 3% by weight to about 8% by weight. By way of contrast,
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`in those portions of the system where the temperature is typically higher, such as at the
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`compressor discharge and in the condenser, the viscosity of the lubricant is lower because
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`of the higher temperatures. As a result, in most cases the lubricant will flow out of these
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`areas even if there is substantial immiscibility between the refrigerant and the lubricant at
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`these temperatures.
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`24.
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`Based on the above analysis, it is possible to evaluate the results reported
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`in Table 1 described above (see Exhibit D). Each of the following pairs were determined
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`to possess miscibility at 0C, 10C, 20C, 30C, 40C and 50C and for lubricant:HFO weight
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`ratios of 20:80 and 50:50 and as a result no miscibility curve was needed or prepared to
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`establish that these pairs are generally useful in refrigerant applications without the need
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`for an oil separator: t—l234ze/PAG ND—8; l234yf/POE RL 32—3MAF; and t—l234ze/POE
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`RL 32—3MAF. For the remaining pairs, miscibility curves were prepared to help explain
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`that the above—noted data establishes these refrigerant/lubricant pairs are either useful or
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`not useful in refrigerant applications if there is no oil separator. It should be noted that
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`the attached miscibility curves are based on and consistent with the data reported in Table
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`1 above. The evaluation of l234yf/mineral oil; l234ze/mineral oil and l234yf/PAG ND-
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`8 is described below:
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`25. With respect to the miscibility of HFO—l234ze with mineral oil, this
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`miscibility curve is attached as Exhibit Thomas A and shows a Dome—shaped curve with
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`no top. This curve indicates that there is no miscibility for this lubricant/refrigerant pair
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`for most of the temperature and concentration ranges of interest for heat transfer
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`applications, and therefore that this pair can not generally be used in heat transfer
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`applications without an oil separator.
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`26. With respect to the miscibility of HFO—l234yf with mineral oil, this
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`miscibility curve is attached as Exhibit Thomas B and shows a Dome—shaped curve with
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`no top. This curve indicates that there is no miscibility for this lubricant/refrigerant pair
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`for most of the temperature and concentration ranges of interest for heat transfer
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`applications, and therefore that this pair can not generally be used in heat transfer
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`applications without an oil separator.
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`27. With respect to the miscibility of HFO—l234yf with PAG, this rr1iscibility
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`curve is attached as Exhibit Thomas C and shows a U—shaped curve with a LCST of
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`about 25C. This curve indicates that there is miscibility for this lubricant/refrigerant pair
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`at all lubricant concentrations below about 25C. The large region of miscibility for this
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`pair at the temperatures and concentrations discussed herein reveals that such a
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`lubricant/refrigerant pair would be useful in most commercial applications without the
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`use of an oil separator.
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`STABILITY
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`28.
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`One of the most important PAG lubricants in use at the time the present
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`invention was made, and continuing through to the present time, is the PAG lubricant
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`manufactured by Idemitzu Kosan and sold under the trade designation ND—8.
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`I have
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`tested and/or supervised the testing of a sample of ND—8 purchased in the retail trade to
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`determine its properties, and I am aware that the properties of ND—8 were reported in the
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`patent literature, namely, U.S. Patent 7,303,693. This information is provided in the
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`Table 2 :
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`TABLE 2 — ND—8 PROPERTIES
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`Property
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`Viscosity,
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`@ EO3PO Ratio
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`Molecular
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`40°C cSt
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`Weight
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`From Testing
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`From ‘693 Patent
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`42.3
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`031
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`930
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`* Number Average Molecular Weight
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`29.
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`This information indicates that the PAG known as ND—8 contains
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`essentially only oxypropylene units and has a kinematic viscosity that would fall within
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`the range of from about 10 to about 200 centistokes (cSt.) at about 37°C.
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`30.
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`The material whose properties were tested and reported in Table l was
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`used to conduct stability testing in combination with several fluorinated olefins, including
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`the preferred fluorinated olefin in accordance with the claims now pending and several of
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`the other fluorinated olefins exemplified in Daikin. More particularly, a mixture
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`comprising about 50% by weight of ND—8 and about 50% by weight of selected
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`fluorinate olefin was formed and placed in a sealed tube with coupons of copper, steel
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`and aluminum. This mixture was then maintained at a temperature of 200C for 36 hours,
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`after which the fluid in the tube was subject to testing to reveal the information contained
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`in Table 3. The procedure described herein and the test results reported below are known
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`and accepted as being indicative of the stability of such compositions for use in
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`refrigeration systems. The results are provided below in Table 3:
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`TABLE 3
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`l243zf
`l234yf
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`Fluoride
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`2.8
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`5
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`l225yez
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`216
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`N
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`5
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`.2
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`2
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`Dimers
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`Yes
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`No
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`No
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`o
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`l26lyf
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`160,000
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`85
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`Not possible to measure
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`3 l.
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`The Fluoride value measured as reported in Table 3 was determined by
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`first preparing the sample in accordance with ASHRE Standard 97-2007 (attached as
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`Exhibit E) and then tested using Ion Chromatography. This value is representative of the
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`amount of free fluorine ions available after testing and is indicative of the stability of the
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`combination being tested, with the higher value being indicative of less stability. While
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`these results do not negate the utility that can be achieved by using the compound HFO—
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`l234ze. as can be seen from Table 2, the HFO—l234yf has a stability as measured by this
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`technique dramatically and unexpectedly superior to that exhibited by the combination of
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`this oil with the structurally similar compound HFO— l234ze.
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`32.
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`The Total Acid Number (TAN) value measured as reported in Table 3 was
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`determined using ASTM D 974-06. This value indicates the Total Acid Number after
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`testing, with the higher value being indicative of less stability. Once again, while these
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`results do not negate the utility that can be achieved by using the compound HFO—
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`l234ze, as can be seen from Table 2, HFO—l234yf has a stability as measured by TAN
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`which is also unexpectedly superior to that exhibited by the combination of this oil with
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`the structurally similar compound HFO—l234ze.
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`33.
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`The column labeled “DIMER” in Table 3 was determined using NMR
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`Spectroscopy. This result indicates whether or not dimerization of the fluorinated olefin
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`in the presence of the lubricant was occurring, which is indicative of not only the stability
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`of the combination, but also its potential to create components that may have a
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`deleterious effect on the operation of many air conditioning systems. As can be seen by
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`the results reported in the “Dimers” column of Table 3, there was a substantial absence of
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`dimers produced in the ND—8/HFO—l234yf combination. This stands in contrast with the
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`fluorinated olefin HFO—l243zf.
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`EXHIBIT THOMAS A
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`TO DECLARATION OF RAYMOND H. THOMAS
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`PH1 3132772v1 07/05/12
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`Miscibility of HFO—1234ze and
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`Napthenic Mineral OIL (C3)
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`% Mineral Oil in Mineral Oil/HFD-12341e Mixture
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`EXHIBIT THOMAS B
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`TO DECLARATION OF RAYMOND H. THOMAS
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`PH1 3132772v1 07/05/12
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`Miscibility of HFO-1234yf and
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`Napthenic Mineral OIL (C3)
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`Miscibility of HFO-1234yf with Napthenic Mineral Oil (C3)
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`100 V
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`% Oil in Refrigerant/Mixture
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`EXHIBIT THOMAS C
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`TO DECLARATION OF RAYMOND H. THOMAS
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`PH1 3132772v1 07/05/12
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`HFO-i1234yf Misciblity Critical Solution Temperatures
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`with PAG (ISO 46) Lubricant
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`idemitsu ND—8
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`IIf
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`/"
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`iI
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`I’fI
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`II
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`I
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`7"/
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`;’‘I
`,1/2.’
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`J’1
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`.4’/
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`2
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`ae“““°
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`immiscible Region
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`M,/V/K’ '
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`90
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`80
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`70
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`B0
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`50
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`40
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`30
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`20
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`Miscible Region
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`Temperature,