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Materials for oxygen service

Robert Lowrie The BOC Group A research engineer opens the valve of an oxygen cylinder and, almost immediately, a fire burns through the metal body of the attached pressure regulator. Fortunately, the discharge is directed away from the engineer and he is only slightly burned. Most materials can burn in oxygen. The higher the concentration, pressure and temperature of oxygen, the more likely this reaction and the more violent it is apt to be. The materials that do not burn in oxygen are the ceramic oxides, inert metals (e.g., gold and platinum) and noble gases. Materials of construction for oxygen service must have a wide variety of properties. Unfortunately, many of these materials burn in oxygen. Sources of ignition For a fire to occur, oxygen, a fuel and an ignition source are needed. Since one must use some materials that can burn in oxygen, the key consideration is the intensity of the ignition source in relation to the ignitability of the materials used. Some of the more common sources of ignition: 1. Rubbing friction, which caused ignition of the liquid-oxygen pump (see the top photo of the figure) when the impeller rubbed against the casing. 2. Heat of compression, which can add a lot of heat to a gas that is suddenly compressed. This happens when a low-pressure gas is rapidly pressurized by addition of a high-pressure one. In a nitrogen regulator that had been improperly converted to oxygen use (see the center photo in figure), oil was ignited when the heat of compression increased the temperature. 3. Mechanical impact, which, for example, can cause asphalt pavement covered with liquid oxygen to explode when a hammer is dropped on it. The liquid-oxygen line (the bottom photo of the figure) was ignited when an overpressurized bellows ruptured, mashing aluminum-foil insulation against the outer pipe, igniting the foil. 4. Particle impact, which has been shown to ignite a pipeline, especially at an elbow 1 or other part that changes direction. 5. Static electricity (electric arc), which can create high temperatures that give rise to ignition at the arc. Testing for oxygen compatibility Materials differ greatly in their ease of ignition and in their intensity of combustion in oxygen. Several tests are used to measure these properties: Heat of combustion is measured in a calorimeter, according to ASTM D2382 2. The less heat that is given off, the less likely is ignition, and the less energy will be available to propagate combustion through the material or to adjacent materials, which is called promoted ignition. Table I contains heats of combustion for typical materials. (In all tables, manufacturers and tradenames are given, since data vary somewhat by product. This is not meant to serve as a listing of all materials sources, but rather as a means of comparison of materials.) Polyethylene has a high heat of combustion and would seldom be a choice for an oxygen system. Polytetrafluoroethylene (PTFE) has a low value and is often used. At its autoignition temperature, a material ignites when heated in a given oxygen atmosphere. ASTM Standard G72 3 describes the procedure for performing tests to 20.7 MPa (3,000 psi). A typical hydrocarbon oil or grease ignites at about 180C (see Table II), while a silicone grease ignites near 215C, and some fluorocarbon oils and greases ignite above 425C, the maximum temperature used in ASTM G72. The mechanical impact test, ASTM D2512 4, employs a standard weight that is dropped a known distance to hit a striker pin. The pin rests on the specimen, which is usually immersed in liquid oxygen. Pressurized oxygen gas can be used instead (ASTM G86 5). The material is considered oxygen compatible if there are no reactions in 20 tests. Table III contains typical results. In the gaseous-fluid impact test, ASTM G74 6, a sample at the closed end of a tube is subjected to a sudden rise in oxygen pressure as the valve to an accumulator is opened, strongly heating the gas. For example, in theory, adiabatically compressing oxygen from 1 atm to 13.8 MPa (a common pressure used in cylinders), will heat it to 945C (1,730F). This test is used for materials for valve seats, tubing, and other constructions that undergo dead-end compression. In the oxygen index test, ASTM D2863 7, an oxygen-nitrogen mixture flows upward past a strip-shaped sample, which is lighted at its top. The oxygen index is the minimum percentage of oxygen needed to allow the sample to burn steadily downward. Some typical values are: PTFE O 100; fluoroelastomers, 57; silicone rubbers 2829; nylon 6/6, 24; cotton, 18; and polyethylene, 17.5. Selection criteria A procedure, Evaluating Nonmetallic Materials for Oxygen Service, presented in ASTM G63 8, is often used in selecting materials. In following this method, the application is looked at for the probability of a significant ignition event (or events): Could rubbing occur if a part failed or moved? Could there be dead-end compression? Etc. Next, the possible effects of ignition are considered: How might it damage the system or nearby equipment? More importantly, could people be injured or killed? Then, for each in a list of materials that might be suitable for the particular application, test data showing ease of ignition at operating conditions and ability to promote ignition of other materials are evaluated. Finally, one's experience of similar applications is considered, along with the costs and availability of the materials. Selection often involves much subjective judgment and compromise. An example will illustrate the process. Example: gasket selection A gasket is to be chosen for sealing the flanges that join the discharge line from a 6.2MPa (900 psi) centrifugal compressor for oxygen with a carbon-steel pipeline. The gas temperature may rise to 150C (300F). The compressor is remotely located and unattended. The likelihood that any of the usual ignition mechanisms will occur is remote. If, nevertheless, the gasket is somehow ignited, this may, in

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turn, ignite the steel flanges and pipe. However, if the heat of combustion of the gasket material is low, ignition of the flanges will be unlikely. This is because the massive flanges can absorb considerable heat without reaching their kindling temperature. There would be no danger to personnel in case a fire would occur since the equipment would be unattended. Damage would be limited, since the fire would stop as the pressure dropped. The damage could be repaired rapidly. Although delivery of the product would be interrupted until the repairs were completed, a backup storage system would meanwhile allow operation to continue. A range of gasket materials is available. Of these, natural and synthetic hydrocarbon-rubbers have high heats of combustion and are undesirable. The silicone rubbers have lower, but still too high, heats of combustion. Two classes of gasket materials have low values the fluorocarbons (plain and reinforced) and compressed asbestos bonded with synthetic rubber. The asbestos gaskets are considerably cheaper and have a history of successful use in oxygen pipelines. Thus, they are chosen for this service. Bonded asbestos in a permanent joint presents a minimal health risk. Typical materials used Here, we will look at components and materials commonly found in an oxygen-handling system: Valve seats are crucial. Ignition of a valve seat can occur from adiabatic compression, high-velocity particle impact, or rubbing of the seat on closing. Metal-to-metal valve closures are very resistant to ignition if the metals or alloys are of nickel or copper. PTFE, polychlorotrifluoroethylene (PCTFE) and their composites with inorganic reinforcements and fillers resist ignition, although some reactions have occurred. Nylon 6/6 has excellent sealing properties and is used for seats in the majority of oxygen valves. However, ignition of these seats occasionally occurs. If the fire is confined to a seat, the consequences of an ignition are not usually severe. Whether combustion will be so limited will depend on the size of the nylon seat (the smaller the better), and the design of adjacent parts and their materials of construction. Heavy copper-alloy parts usually resist promoted ignition from a burning nylon seat. Packing materials For low to moderately elevated (150C or 300F) temperatures, PTFE is an excellent choice. Since packing is well confined, cold flow of the PTFE is not a problem. Gaskets are made in a wide range of materials appropriate for oxygen service. However, selection can be complicated by requirements other than just oxygen compatibility. PTFE offers good oxygen compatibility, but it exhibits cold flow and may allow leaks. Composites of PTFE reinforced with inorganic particles or fibers are almost equal in compatibility and better in resisting cold flow. PCTFE is also more resistant to flow than PTFE, but it is more expensive. Polyimide/graphite-fiber composite and flexible graphite are quite resistant to ignition and are sometimes used, despite their high heats of combustion. Adhesive-backed flexible graphite, however, should not be used in oxygen service. Compressed-asbestos-fiber gaskets that are bonded with a synthetic rubber have performed well. However, autoignition temperatures are relatively low (150200C or 300390F), which limits their use. Asbestos has often been the resilient material used in metal-jacketed or spiral-wound gaskets; it has good oxygen compatibility and is usable to at least 260C (500F). As asbestos is being phased out for many uses, PTFE and resilient inorganic fibers may replace it in many of the above gasket formulations. Thread sealants may be of several types, each having its advantages and problems, and requiring precautions for safe use. PTFE tape (only from virgin material) works well. Like all thread sealants, it should be applied only to the male threaded part and never to the first thread. This is so that no sealant gets inside of the threaded joint, where it would be exposed to more-severe impact or vibration. Inorganic thread compounds, such as sodium silicate plus clay or talc, are highly oxygen-compatible, but they set hard and may not seal as well as softer materials. Sealants having good oxygen compatibility are made with PCTFE fluids and fillers such as PTFE particles, kaolin or lead powder. A strong reaction may occur when a reactive metal (e.g., aluminum, magnesium or titanium) is exposed to a PCTFE fluid, and strong surfacepressure and shear. Thus, sealants containing PCTFE fluids should not be used on threaded parts of these metals, since rubbing during thread rotation may initiate a reaction. Lubricants Hydrocarbon oils and greases have poor oxygen compatibility. They are easily ignited and have high heats of combustion and, thus, should not be used in contact with oxygen or any oxygen-rich atmosphere, even at atmospheric pressure, as in a vacuum pump that handles oxygen. Triaryl phosphate fluids are used in vacuum pumps, although reactions occasionally occur. Silicone lubricants, while somewhat superior to hydrocarbons, are still poorly compatible and should not be used for oxygen service. The only oils and greases with good oxygen compatibility are those based on fluorocarbon fluids. There are two types. The first is based on chlorotrifluoroethylene polymer fluids; the second, on perfluoropolyethers. These materials have high autoignition temperatures (see Table II) and low heats of combustion. As was mentioned under thread sealants, these fluorocarbon lubricants should not be used on alloys of reactive metals such as aluminum. Structural plastics, other than fluorocarbons, are to be avoided in oxygen service, due to poor oxygen compatibility. Adhesives, other than inorganic silicates or phosphates, have poor oxygen compatibility. If an adhesive is needed, special precautions should be taken to ensure that no trace of it is on an exposed surface that may be subject to rubbing, impact or other mechanism that can promote ignition. Metal compatibility Of the oxygen compatibility tests above, only heat of combustion is appropriate for evaluating metals. Based largely on experience, a list (Table IV) of groups of metals can be drawn up in order of decreasing oxygen compatibility. Only the position of aluminum, whose ignition depends upon breaching its oxide coating, might be controversial. However, Table IV does not distinguish between the alloys in a class e.g., brass vs. aluminum bronze, or Inconel 600 vs. Inconel 750. Further, the table does not address responses to various ignition sources. Fortunately, the U.S. National Aeronautics and Space Administration (NASA) has funded a program at its White Sands, N.M., Testing Facility to develop a group of tests appropriate for evaluating oxygen compatibility of metals and alloys. Three tests are under development: frictional heating, promoted ignition and particle impact. NASA has presented a preliminary report on these tests and is continuing research, which focuses on alloys for use in the space program. Also, ASTM

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Committee G-4 on Compatibility and Sensitivity of Materials in Oxygen-Enriched Atmospheres, along with the Compressed Gas Assn. (Arlington, Va.) and private corporations have begun a testing program at White Sands for industrial alloys and coatings. Design precautions As mentioned earlier, it is impossible to build noncombustible oxygen systems. Thus, it is essential to take precautions in addition to selecting the most suitable materials. Here are examples of some typical design procedures, which are covered more fully in ASTM G88-84 9: 1. Design the system to avoid unnecessarily elevated temperatures and to dissipate heat effectively. Avoid overly high oxygen pressures by reducing the pressure at the oxygen-supply inlet to keep intermediate components at a minimum pressure. 2. Design a system that is easy to regularly clean and maintain. Use rugged, highly fire-resistant filters where oxygen enters the system, where particles may be generated, and before areas of high velocity, e.g., throttling valves. 3. Limit gas velocities 10 and use highlyfire-resistant materials where velocities must be high or where gas-stream impingement occurs. 4. Use slowopening valves, small bypass valves and line restrictors to avoid rapid pressurization and dead-end compression. 5. Design to avoid friction and rubbing, by providing assured positive clearances for moving parts. 6. Provide monitoring equipment to detect unfavorable changes in operating conditions, and use automatic shutdown devices, which are triggered by sensors on bearings, heaters, etc., in case of emergencies. 7. Design to manage fires by such means as installing bulk oxygen storage at a remote location; isolating or erecting barriers around critical equipment to contain a fire or explosion; and providing remote shutoffs for valves and equipment. 8. Anticipate the effects of an oxygen release into the surrounding area by venting or accident. In brief, respect oxygen in all applications. Read literature on oxygen compatibility and safety, using the references presented here as an introduction. Give careful consideration to the possibility for ignition of an oxygen fire in equipment. Choose materials based on oxygen compatibility, industry experience, the material's ability to meet service requirements, and cost. If a new system is to be built, consider calling a specialist in oxygen compatibility to assist in design choices and check over the proposed setup. Richard Greene, Editor References 1.Wegener, W., Stahl u. Eisen, Vol. 84, No. 8, pp. 469-475, Apr. 9, 1964. 2.ASTM D2382-80, ``Test Method for Heat of Combustion of Hydrocarbon Fuels by Bomb Calorimeter,'' ASTM, Philadelphia, 1986. 3.ASTM G72-82, ``Test Method for Autogenous Ignition Temperature of Liquids and Solids in a HighPressure Oxygen-Enriched Environment.'' 4.ASTM D2512-82, ``Test Method for Compatibility of Materials with Liquid Oxygen (Impact Sensitivity Threshold and Pass-Fail Technique).'' 5.ASTM G86-84, ``Test Method for Determining Ignition Sensitivity of Materials to Mechanical Impact in Pressurized Oxygen Environments.'' 6.ASTM G74-82, ``Test Method for Ignition Sensitivity of Materials to Gaseous Fluid Impact.'' 7.ASTM D2863-77, ``Measuring the Minimum Oxygen Concentration to Support Candle-Like Combustion of Plastics (Oxygen Index).'' 8.ASTM G63-83a, ``Guide for Evaluating Nonmetallic Materials for Oxygen Service.'' 9.ASTM G88-84, ``Guide for Designing Systems for Oxygen Service.'' 10.Pamphlet G-4.4, ``Industrial Practices for Gaseous Oxygen Transmission and Distribution Piping Systems,'' Compressed Gas Assn., Arlington, Va., 1980. 11.''JANAF Thermochemical Tables,'' 2nd ed., NSRDS-NBS 37, Natl. Bureau of Standards, 1971. 12.Smithells, C. J.., ``Metals Reference Book,'' 5th ed., Butterworths, London, 1976. Biography Robert Lowrie is senior research metallurgist at the Technical Center, The BOC Group, Inc., 100 Mountain

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Ave., Murray Hill, NJ 07974. Tel: (201) 464-8100. He has had over 30 years' experience in various areas of metallurgy, failure analysis and materials selection. For the past eight years, he has also specialized in the compatibility of materials with oxygen. A graduate of Pennsylvania State University with B.S. and Ph.D. degrees in metallurgy, he is chairman of ASTM Committee G04 on Compatibility and Sensitivity of Materials in Oxygen-Enriched Atmospheres. He is also a member of the American Welding Soc., Tau Beta Pi and Phi Lambda Upsilon. Before joining BOC, he worked for Union Carbide Corp., Northrop Corp., and OwensCorning Fiberglas Corp.

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