THE NIST WORKSHOP
100 On 22 September 1988, the National Institute of Standards and Technology ('NIST'), a part of the United States Department of Commerce, conducted a workshop on property data needs for ozone safe refrigerants. The purpose of the workshop was to identify the need for thermodynamic and transport property in data constructing replacements for those refrigerants that damage the ozone layer in the upper atmosphere. Approximately thirty experts from industry, government and universities participated in the workshop. Among those who attended was Mr Richard Powell of the Research and Technology Department of ICI in England.
101 A summary of the discussion sessions at the workshop ('the Summary') was prepared and circulated to participants. Extracts and summaries of papers delivered in the course of the workshop were also made available to participants.
102 The Summary recorded that the workshop was convened in order to inform industry of the progress of research begun at NIST in early 1988 into measurements of the thermo physical properties of promising alternative refrigerants such as R-134a, R-123 and R-141b. The Summary also stated that the workshop was convened principally to solicit industry input into the directions and priorities for further work in that area. The Summary recorded that, following several prepared presentations, those in attendance divided into two discussion groups, each of which addressed five specific topics, namely:
1. What refrigerants should be considered?
2. Should mixtures be planned for, and if so which ones?
3. What properties should be measured, at what accuracy level, and in what format should the data be presented?
4. What is industry doing now and what are they willing to provide in the future?
5. What organisations have experimental expertise?
103 The Summary set out conclusions under those heads. The conclusion under the first two heads, relevant for present purposes, were as follows:
'1. What refrigerants should be considered?
Refrigerants 134a, 123 and 141b, the alternative fluids under active development, were taken as given. Additional fluids proposed were:
R32
R124 (particularly in centrifugal applications)
R125
R134
R142b
R152a (proposed as component of mixtures)
R23 (proposed as component of mixtures)
Several specific needs in search of a fluid were also identified:
- Commercial (e.g. supermarket) refrigeration systems currently using R502 were identified as a high priority application; R32 and R125 (or mixtures thereof) were considered likely candidates.
- Other substitutes for R12 should the efficiency of R134a indeed prove lower.
- Substitutes for R22 in the event that it is regulated in the future. There were some, however, who felt that R22 substitutes should not be discussed; they argued that even a rumor of a likely R22 substitute would strengthen the position of those wanting to restrict it.
All of the above fluids were for refrigeration applications; no fluids beyond R123 and R141b were identified for foam blowing applications.
Beyond the above near-to-mid-term alternatives there was some discussion on long-range possibilities, including the need to develop a second generation of alternatives for maximum possible energy efficiency. Although no specific fluids were identified, fluorinated ethers, 3-carbon halocarbons and refrigerant mixtures were mentioned as possibilities. It was agreed that fluids which underwent a "wet compression" would not be acceptable for compressors having valves (e.g. piston-type compressors) but such fluids could not be ruled out in other types of compressors.
2. Should mixtures be planned for, and if so which ones?
Azeotropic mixtures were felt to be acceptable for many applications with nonaeotropic mixtures viewed with suspicion; near-azeotropic mixtures received an intermediate reception. Although there was much disagreement on specifics there was a consensus that mixtures should be investigated, with the use of nonazeotropic mixtures an open question.
Mixtures were viewed as a good possibility in refrigerators, especially if they would yield higher COPs than single-component fluids. One group identified large chillers as one possible application for nonazeotropic mixtures while the other indicated that mixtures would present problems in large equipment. Nonazeotropic mixtures were viewed as not acceptable for use in automotive air-conditioning. One explanation offered for the reluctance to accept mixtures was simply lack of familiarity on the part of the mechanical engineers who normally design refrigeration equipment.
Specific mixtures suggested were:
Near-azeotropic mixtures:
R22/152a
R22/142b
R134a/152a
R32/124
R32/125
Nonazeotropic mixtures:
R23/152a
R32/124
The first three mixtures listed above were suggested for use in refrigerators.
The difficulties presently encountered in modelling highly polar mixtures (i.e. mixtures of the hydrogen-containing refrigerants) could be reduced significantly given a set of accurate thermophysical property data for a reference mixture.'
104 One of the prepared presentations was by Messrs Mark O. McLinden and David A. Didion entitled THERMOPHYSICAL PROPERTY NEEDS FOR THE ENVIRONMENTALLY-ACCEPTABLE HALOCARBON REFRIGERANTS ('the McLinden Paper'). The abstract of the McLinden Paper was in the following terms:
'The need for, and uses of thermodynamic and transport properties in the selection of working fluids for the vapour compression cycle and in equipment design are reviewed. A list of hydrogen-containing halocarbons, as well as their mixtures, are presented as alternatives to the environmentally-harmful, fully-halogenated chlorofluorocarbons. These fluids range from well-characterized, widely-available refrigerants to materials available only by custom synthesis about which very little is known. Data priorities for these fluids are presented; most essential are critical point, vapor pressure, liquid density, ideal gas heat capacity, and vapor p-V-T data. A critical need exists for these data on a number of candidate working fluids in order not to lose the opportunity to select the best set of future refrigerants.'
105 The introduction section of the McLinden Paper states that CFCs are a class of compounds containing the halogens chlorine and/or fluorine on a carbon skeleton. The major CFC refrigerants are characterised by their non-flammability, low toxicity, good thermal properties and extreme stability. That last characteristic, which had previously been considered an asset, was then seen to be a liability. The introduction states that CFCs are responsible for approximately 15 to 20 per cent of the predicted global warming trend. Reference was then made to the International Protocol to limit the production of certain CFCs that was negotiated at Kyoto in 1987 and refers to the restrictions on the production of CFCs that some countries have announced. The impending restrictions were said to have created new urgency in research for replacement fluids.
106 The introduction then stated that, to be acceptable as a refrigerant, a fluid must satisfy a variety of criteria as indicated below:
'Chemical:
Stable and Inert
Health, Safety and Environmental:
Nontoxic
Nonflammable
Does not degrade the environment
Thermophysical Properties:
Critical point and boiling point
Temperature, appropriate for the application
Low vapor heat capacity
Low viscosity
High thermal conductivity
Miscellaneous:
Soluble in lubricating oil
High vapor dielectric strength
Low freezing point
Compatible with common materials
Easy leak detection
Low cost'
107 Section 2 of the McLinden Paper is headed 'THERMOPHYSICAL PROPERTIES IN THE VAPOR COMPRESSION CYCLE' and contains the following relevant material:
'2.1 Thermodynamic Properties
Thermodynamic properties determine the efficiency and capacity of the cycle and thus are the key data needed in designing refrigeration equipment and in comparing one refrigerant with another. Of prime importance is the energy involved in the various processes, thus the need for accurate enthalpy values. … Also important are the operating pressures of the condenser and evaporator; these are largely a function of the vapor pressure. …
Pressures and densities in themselves need be known to an accuracy of only a few percent. …
2.2 Transport Properties
…
2.3 Data Format
To be useful to the design engineer, thermophysical property data must be in the proper format. …Tables listing properties for the saturated liquid and vapor states at even increments of temperature are the most common and widely used format. As a minimum, these include vapor pressure, liquid and vapour density…, and liquid and vapour enthalpy and entropy. Also desirable is a tabulation of viscosity, thermal conductivity, isochoric and isobaric specific heats, and sonic velocity for the saturated liquid and vapor states and surface tension as a function of temperature.'
108 In Section 3, under the heading 'STATUS OF THE ENVIRONMENTALLY-ACCEPTABLE REFRIGERANTS' the McLinden Paper lists, in order of normal boiling point, the components that might replace CFCs. The McLinden Paper then goes on to say, relevantly, as follows:
'Three fluids are currently the focus of intense development efforts, both by the chemical producers and refrigeration equipment manufacturers. R134a, the most publicized new refrigerant, shows promise as a replacement for R12, particularly in refrigeration and automotive air-conditioning applications. R123 and R141b are being developed as replacements for R11;… The use of R123 as a refrigerant in centrifugal-type compressors appears feasible while the evaluation of R141b in this application has been seriously hampered by a lack of thermodynamic data. Both R123 and R141b are available in limited quantities, the former as a specialty chemical and the latter as a byproduct of the R142b process.
There are several additional compounds that warrant consideration, both in terms of their properties and prospects for eventual commercial availability…'
109 After referring to R-123, R-123a, R-124, R-125 and R-143a as possible candidates, reference is made to R-32 and R-134 and R-134a. The McLinden Paper then states that there are several reasons to expand the list of considered fluids beyond the R-134a, R-123 and R-22 'that are most often discussed'. Reasons are given.
110 Reference is then made to hydrogen-containing halocarbons, listed according to their flammability and chlorine content. The McLinden Paper then states that at least a dozen halocarbons are candidates and goes on to say:
'Toxicity testing is, however, incomplete for several of these compounds; in particular, there are concerns about potential toxicity problems with R123 and R141b. If, however, a non-flammable, chlorine-free (zero ozone depletion potential) fluid is required, the list is shortened to four.'
The four shown are R-134, R-134a, R-125 and R-23. However, R-23 is said to have a boiling point 'Far too low for most applications'.
111 Section 4 of the McLinden Paper is entitled 'DATA PRIORITIES' and begins with the statement that 'there is a critical need for at least skeleton data on a variety of potential halocarbon refrigerants'. The McLinden Paper then lists the thermophysical property data needed to allow an assessment of a refrigerant. The data are categorised and prioritised as follows:
- 'Zero Order': Information that is the minimum necessary to screen a large number of candidate fluids.
- 'Group 1': The core thermodynamic information necessary to fit most equations of state, thus allowing an accurate evaluation of the performance of a fluid in refrigeration equipment.
- 'Group 2 and Group 3': The basic transport properties needed for equipment design and to allow refinement of the thermodynamic formulation.
- 'Group 4': Measurements that provide a much more extensive and complete characterisation of a fluid.
112 A table then sets out information available under each of those five groups in relation to twelve environmentally acceptable halocarbons, including R-143a, R-125 and R-32. The table indicates that, for the mot part, there was no data for R-143a, R-125 and R-32 in respect of Groups 1, 2, 3 and 4; the only data available for those compounds was limited, of questionable accuracy, or referred to isolated points. That is to say, much of the critical data necessary for the assessment of those compounds was not available at that time.
113 After referring to the lack of data in relation to mixtures and the need for such data to allow an assessment of near azeotropic mixtures as CFC replacements and to aid in the identification of possible azeotropic mixtures, the McLinden Paper concludes as follows:
'A set of hydrogen-containing halocarbons have been identified as the most promising fluids to replace the fully-halogenated CFC refrigerants. Thermophysical property data on these fluids is critically needed in order not to lose the opportunity to develop the best set of working fluids and to permit the design of efficient refrigeration equipment using them. The fully-halogenated CFCs now appear to be doomed as important industrial chemicals, yet… most of the properties work on refrigerants is still concerned with fully-halogenated fluids. The fluid properties community would do a great service by turning their attention to the environmentally-acceptable working fluids.'
114 The overall impression to be derived from the material concerning the NIST workshop, as summarised above, is that there was a critical need for much more information in relation to numbers of possible compounds. While some of the compounds involved in the mixtures of the Ternary Application and the Binary Application are referred to, it is clear that the material does not point in any unequivocal manner towards any of the mixtures of the Ternary Application or the Binary Application.
115 While the Summary states that R-32 and R-125, or mixtures thereof, were considered likely candidates for refrigeration systems currently using R-502, any such mixture was no more than a hypothetical possibility. It is by no means clear from the reference to those refrigerants as to whether a mixture of R-32 and R-125 was being suggested or whether it was being suggested that a mixture of R-32 and some other refrigerant, on the one hand, and R-32 and some other refrigerant, on the other hand, were being put forward as likely candidates. The summary does not clearly point to the mixtures of the Binary Application.