The Effect Of Moisture On POEs

January 31, 2004
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Good refrigeration practice dictates that the moisture level in a refrigeration system must be carefully controlled. Effective measures for moisture control using POE lubricants have been developed and are in wide commercial use.

Polyolesters (POEs) are a family of synthetic lubricants manufactured by reacting an alcohol with an organic acid to form a single molecule.

The manufacturing process involves the reaction of a mixture of organic acids with one or more alcohols to give the desired polyolester. The reaction is carried out at an elevated temperature and water is constantly removed. The reaction is driven to completion with virtually no acids or alcohols remaining.

There are many types and grades of esters, and it is therefore important to understand that all esters are not the same. Several important properties of esters affect their performance as lubricants.

These include lubricity, miscibility, viscosity, solubility, and moisture content.

Hygroscopicity And Moisture

Hygroscopicity is a term used to describe a lubricant's and/or refrigerant's affinity for moisture. HFC refrigerants and POE oils have a polar molecular structure, which attracts the polar water molecule. Therefore, the solubility of water in HFCs and HCFCs is many times greater than in the CFCs they replace.

POEs are also hygroscopic and can pick up more moisture from their surroundings and hold it much tighter than the previously used mineral oils. The rate that POEs pick up moisture depends on temperature, relative humidity, exposure time, and relative surface area. (See Figure 1.)

Moisture can enter the refrigeration system by a number of routes:

  • Improper vacuuming of the system.

  • System leaks.

  • System components; at elevated temperatures water can leach out of elastomeric or plastic system components and be reabsorbed when the system cools down.

  • Improper handling of refrigerant.

  • Improper handling of POE lubricants.

  • Saturated or malfunctioning drier.

    Figure 1. Typical moisture uptake curve of a typical Emkarate RL lubricant at a range of relative humidities (RH) at ambient temperature.


    Measuring Moisture

    Karl Fischer titration has be-come the accepted standard method for laboratory determination of moisture in refrigerants and lubricants. The technique is particularly simple when analyzing oil samples; it involves weighing the sample, introducing the sample into the titration vessel, and reading the mass of moisture in the sample.

    The mass is typically given by the titrator in micrograms. Dividing by the sample weight gives parts of water per million (ppm) of lubricant.

    It is important that the introduction of moisture into a system is minimized and the removal of the moisture takes place effectively. At high levels of moisture, the performance of the refrigeration system may be adversely affected.

    Water can interact with:

  • Refrigerants, forming clathrate hydrates. Clathrate hydrate solids form when water molecules are linked through hydrogen bonding, creating cavities that can enclose various guest molecules (also known as hydrate formers). The formation, nucleation, growth, decomposition, structures, properties, and thermodynamic phase equilibria have been reported from a number of hydrate formers, including HFC refrigerants such as R-32, -125, -134a, -407C, and -410A.

  • Polyethylene terephthalate (PET), leading to embrittlement and hydrolysis of polyester materials.

  • POE lubricant and/or refrigerant, leading to acid formation.

  • Copper. One possible cause of copper plating is moisture reacting with refrigerant to form an acidic solution. The acids then dissolve or leach copper from components in the A/C system that are copper or contain copper-based alloys, such as brass or bronze. Copper plating also can be caused by contaminants other than water.

  • Steel, leading to corrosion.

  • Cold spots, forming ice crystals.

    If these interactions take place, they can lead to the following losses in system performance:

  • Reduction in effectiveness of the heat exchanger (evaporator) due to ice deposition on the inside surface, thus reducing the area of heat transfer and causing insufficient boiling. This results in a reduced refrigeration effect and eventually lowers the system COP.

  • Expansion valve sticking.

  • Corrosion of metallic materials inside the system.

  • Blockage of the expansion devices due to ice formation.

  • Copper plating.

  • Poor lubrication.

  • Degradation of wire coating.

  • Degradation of motor insulation material.

  • Suction/discharge valve sticking.

  • Plugging of the liquid-line filter-drier.

  • Plugging of the suction filter or heat exchanger (clathrate formation).

    POE lubricants below their moisture saturation limit (approximately less than 3,000 ppm) contain no free water; ice crystals are therefore unlikely to form.

    Hydrolysis

    Hydrolysis is the reverse of the esterification process, in which water reacts with ester to form the original organic acid and alcohol.

    The degree of hydrolysis is driven by the amount of water present. A higher moisture level will lead to a higher degree of hydrolysis. The speed at which hydrolysis occurs depends on the temperature of the system and the acid value. (Acids can act as a catalyst.) It also has been demonstrated that certain additives, high initial acid values, and impurities inside the system can catalyze this reaction.

    For hydrolysis to occur, a sufficient amount of water must exist in the refrigeration system at an elevated temperature (greater than 80 degrees C). Even at relatively high moisture contents, hydrolysis is insignificant at ambient temperatures. When the water content of the system is low, hydrolysis does not occur.

    If the system contains extreme moisture levels (in excess of 500 ppm) and is operating with discharge temperatures in excess of 170 degrees, the system will exhibit its own operational problems, especially within a low-temperature plant.

    Is hydrolysis of ester lubricants a common occurrence? Actually, no. The concern has arisen as a result of several hydrolytic stability tests, which have been conducted in the laboratory at very high water levels (greater than 2,000 ppm) and highly elevated temperatures. That is an order of magnitude greater than expected or seen in the oil under normal operating conditions.

    While there is a theoretical potential for hydrolysis in refrigeration systems, this is severely restricted by the lack of available water. It is suggested that the level of water in the system after assembly be maintained below the equivalent of 500 ppm in the lubricant, preferably below the equivalent of 100 ppm in the system. In addition, the water drying rates with suitable-capacity driers containing molecular sieve are extremely rapid even for wet systems.

    Figure 2. Water pulldown rate for a molecular-sieve drier in a hermetic system.

    How To Remove Moisture

    Moisture can be removed from a refrigeration system by applying a vacuum.

    POEs hold moisture more tightly than mineral oil. But in the case of R-134a, the refrigerant effectively competes with the ester lubricant in partitioning the water (i.e., the water moves from the lubricant to the refrigerant).

    Approximately 50 percent to 60 percent of the moisture injected into an air conditioning system remains in the refrigerant. The rest mixes with the compressor oil.

    The inclusion of a drier in the refrigeration system reduces the equilibrium moisture content of both refrigerant and lubricant phase. Moisture is quickly and efficiently removed by the drier, which yields dramatic drying (pulldown) rates. (See Figure 2.)

    During servicing of the refrigeration system, the use of a filter-drier with a high percentage of molecular sieve will reduce the chance of water contamination of various system components (in particular, the expansion device and evaporator).

    Drier Selection

    The ability to remove water from a refrigeration system is the most important function of a drier. By minimizing the free water in the system, the ability of acids to form or hydrolysis to take place is greatly reduced.

    Here are some of the main influences on drier selection:

  • Molecular-sieve driers are better at removing moisture than alumina driers.

  • The drier capacity should be high enough to remove all moisture in the system.

  • A 100-percent molecular-sieve drier has no capacity to adsorb acids. Alumina driers do, however. Alumina has the ability to react with system fluids. Should system acid levels become too high, the addition of a temporary 100-percent activated-alumina suction filter-drier can be the most effective treatment (leaving the liquid-line drier free to maximize system drying by using 100-percent molecular sieve).

  • POE oils are polar molecules and thus can be adsorbed by the alumina. Therefore, a filter-drier made of this substance can become saturated with oil and is no longer capable of removing acids from the system.

    Alumina may catalyze the hydrolysis of POE lubricants, creating organic acids since both water and lubricant are adsorbed into the pore openings of the alumina. However, provided the filter is not saturated, these acids may remain bound to the drier once they are formed.

  • Driers containing alumina can remove the antiwear additives from certain refrigeration lubricant formulations.

    Different OEMs recommend a variety of drier materials based on the above selection criteria and the oils they have approved. Several OEMs quote acceptable levels of alumina in mixed drier systems, while others recommend 100-percent alumina or 100-percent molecular-sieve driers. You need to refer to the OEM's recommendations when selecting the proper drier.

    ASERCOM, the industry's global compressor organization, recommends the minimum of 70-percent molecular sieve and a maximum of 30-percent activated alumina for liquid-line driers.

    Handling POEs

    Good housekeeping practices should eliminate most potential sources of moisture. These include:

  • Avoid exposing the ester lubricant to air for an extended period of time.

  • Keep containers of ester tightly closed, except when the oil is actually being dispensed.

  • Keep the compressor and refrigeration system components closed, except when work is actually being performed on the equipment.

  • Make sure to keep esters in their original containers.

  • The use of a fresh, appropriately sized liquid-line drier - after servicing a refrigeration system - will reduce the impact of any water contamination.

    This material was jointly prepared by Virginia KMP and Uniqema. For more information, visit www.virginiakmp.com and www.uniqema.com/lubricants/index.htm.

    Publication date: 02/02/2004

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