Perspective on Oxygen Technologies and ASTM G04. Barry Newton WHA International Inc. ASTM G04 - October 10, 2017

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1 Perspective on Oxygen Technologies and ASTM G04 Barry Newton WHA International Inc. ASTM G04 - October 10, 2017

2 Beginnings: ASTM G04 Historical Perspective Dr. Abraham Lapin Air Products and Chemicals, Inc. responding to a CGA Task Force on safety of oxygen regulators and compatibility of materials recognized the need for contribution from outside of CGA February 1975 ASTM G04 was initially formed to assemble researchers and oxygen practitioners from across industry and government Initial ASTM G04 Committee: Chairman W.L. Ball (Air Products and Chemicals, Inc.) Vice-Chairman C.F. Key (NASA Marshall Space Flight Center) Secretary C.E. Johnson (Boeing Company) G04.01 Test Methods Chairman P. Ordin (NASA Lewis Research Center) G04.02 Recommended Practices Chairman R.M. Neary (Union Carbide, Linde Div.) Membership 66 members by 1983

3 ASTM G04 Original Scope Develop and promulgate standard test methods, definitions, recommended practices and classifications for determining the compatibility and sensitivity of materials, materials configurations and applications intended for use in systems subjected to enriched oxygen atmospheres including ignition, combustion, offgassing, reaction products and decomposition tendencies. Enhance the promotion and dissemination of related knowledge. First Guides and Standards: ASTM G63 Guide for Evaluating Materials for Oxygen Service (1980) ASTM G72 Test for Determination of Autogenous Ignition Temperature of Liquids and Solids in a High-Pressure Oxygen-Enriched Environment (1982) ASTM G74 Test to Determine Ignition Sensitivity of Materials by Gaseous Impact (1982)

4 Strategic Plans Developed by 1976 By the committee s third meeting the following matrix was compiled of available ignition and experience which guided rapid development Robert Neary ASTM STP 812 (1983)

5 ASTM G04 Industry Contributions 20 Test Methods and Guides by 1996 Fire Hazards in Oxygen Systems Training by ~1991 ASTM Manual 36 in 2000 ASTM G175 in Standard Technical Publications:

6 The Industry is Changing Should GO4 Scope Change? NASA/Aerospace >> Commercial Space Flight Merger s and Acquisitions (and Divestments): (Really, Really Big Business, 100 bn +) Linde and BOC Air Liquide and Airgas Linde, BOC and Praxiar ( Merger of Equals, $70 bn) Company Market Share (2015) Air Liquide 20% Linde (BOC) 20% Praxair 14% Air Products 12% Airgas 4% TNSC (Taiyo Nippon Sanso Corp) 4% Messer Group 2% Smaller Producers/Distributors ~13%, 11% Company Market Share (2017) Praxair-Linde 33% Air Liquide Airgas 25% Air Products 12% TNSC (Taiyo Nippon Sanso Corp) 4% Messer Group 2% Smaller Producers/Distributors ~24%

7 Some Technology Trends Technology Trends Largely Driven By: Competition for >100 bn (my estimate) Global Industrial Gases Market Emerging Oxygen Technologies like Carbon Capture Emerging Oxidizer (O2, N20) Technologies, Aerospace and Commercial Spaceflight Higher Throughput and Efficiency in ASU Technologies Increased O2 in Carbon Capture Technologies Metals and Glass Refining High Demand for >90% O2 Precious Metals Refining Gold Purification (HNO3+O2) Autoclave System Metals Refining Food Industry Modified Atmosphere Packaging (O2 Mix) Seafood, Oxygenation in Fish Farming Packaged Gases ISO and CGA Taking up Ultra-High Pressure Connections to 800 bar (11,600 psi) Oxygen Cylinders up to 310 bar (4500 psi) available in Europe and Increasing Demand in US

8 Implications for ASTM G04, is our scope still relevant? Other Standardization Organizations ISO promulgating many use standards, very quickly, with very wide subscription Traditional standards organizations (CGA, ASTM, EIGA) supporting/harmonizing EIGA/CGA standards are targeted and specific and they have expertise where they focus ASTM G04 has a different and important role in the industry Back to the beginning Guides and Test Methods Many technologies are new but Industry Needs and Questions haven t changed ASTM G04 still important source for data, testing, and risk analysis technologies ASTM G04 strength has been in solving problems by testing and test methods ASTM G04 test methods are used throughout the industry (our strength) ASTM G04 better at analyzing strengths and limits of our data (statistical analysis)

9 Implications for ASTM G04 (con t) ASTM G04 strength in publishing data and research through the STP series ASTM G04 strength in bringing industry together to solving joint problems Metals Flammability Test Program (Promoted Burning, Friction Ignition, Particle Impact) Heated Metals Promoted Burning Flowing Oxygen Promoted Burning NF3 Materials Compatibility Research Medical Regulator Tolerance Test Requested by FDA NEW: G86 Task Group and Industry LOX MI Testing NEW: Hyperbaric Systems Materials Guide Industry Still Needs Data on Ignition, Combustion, Reactivity, Decomposition Higher Pressures and Temperatures today (greater severity), but Compatibility of materials is still the question Two Additional Focus Areas Need Development Probabilistic Risk Assessments Minimum Ignition Energy of Materials

10 Probabilistic Risk Assessment (quantify ignition probability and potential risk) Examples of questions being asked What mechanical impact energy is required to ignite aluminum cylinder threads (w/ and w/o contamination)?

11 Probabilistic Risk Assessment (quantify ignition probability and potential risk) Questions: What mechanical impact energy is required to ignite aluminum cylinder threads (w/ and w/o contamination)? What size particle (mass > energy) and what particle velocity will ignite particle AND target? 300-micron Carbon Steel Particles Fired at Carbon Steel Target at 600 psig 20 Particles Fired Simultaneously (tight impact distribution) Melting/burning of particles but no ignition of target Particle velocities ~250 fps

12 Enthalpy Change (kj/kg) Temperature ( o C) Probabilistic Risk Assessment (quantify ignition probability (not subjective ranking) and potential risk) Questions: What mechanical impact energy is required to ignite aluminum cylinder threads (w/ and w/o contamination)? What size particle (mass > energy) and what particle velocity will ignite particle AND target? What enthalpy (energy) and rate of increase is needed to ignite material by rapid compression? Gas Temperature Estimates for Rapid Compression Ideal Gas Real Gas WHA Numerical Model Pressure (bar) Enthalpy Calculations for Rapid Compression Enthalpy Change for Ideal Gas Enthalpy Change for Real Gas Enthalpy Change by WHA Numerical Model PTFE Enthalpy Change at AIT Nylon Enthalpy Change at AIT PTFE Starts Igniting about 62 bar (for test conditions) Nylon Ignites at all pressures >40 bar (for test conditions) Pressure (bar)

13 ASTM G04 Original Scope Still Relevant (produce and disseminate data and good practices) Develop and promulgate standard test methods, definitions, recommended practices and classifications for determining the compatibility and sensitivity of materials, materials configurations and applications intended for use in systems subjected to enriched oxygen atmospheres including ignition, combustion, off-gassing, reaction products and decomposition tendencies. Enhance the promotion and dissemination of related knowledge.

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