Cryogenics Safety

Definition and Scope: Cryogenic fluid is a liquid with a normal boiling point below 238F (221R, 150C, 123 K). The safety criteria established in this document apply to the cryogens in use in the facilities, namely liquid helium and nitrogen. Flammable fluids, such as hydrogen, and reactive liquids, such as oxygen and fluorine are excluded. The use of flammable cryogens will require special approval procedures not outlined in this document.

References
GPR 8710.7 Cryogenic Safety

NPD 8710.5, NASA Safety Policy for Pressure Vessels and Pressurized Systems NPR 8715.3, NASA Safety Manual GPR 3410.2, Employee Competence and Quality Management System Training GPR 8621.1, Reporting of Mishaps and Close Calls GPR 8710.3, Certification and Recertification of Ground-Based Pressure Vessels and Pressurized Systems GPR-8730.1, Calibration and Metrology NASA-STD-8719.17, NASA Requirements for Ground-Based Pressure Vessels and Pressurized Systems (PV/S) ANSI Z78.1: Occupational Eye and Face Protection ASTM G63-99: Standard Guide for Evaluating Nonmetallic Materials for Oxygen Service ASTM G88-05: Standard Guide for Designing Systems for Oxygen Service ASTM G93-88: Standard Practices for Cleaning Methods for Materials and Equipment Used in Oxygen Enriched Environments ASTM G94-05, Standard Guide for Evaluating Metals for Oxygen Service
ASTM MNL 36, Guidelines for Oxygen System Design, Material Selection, Operations, Storage, and Transportation CGA Pamphlet G-4.1, Cleaning Equipment for Oxygen Service CGA Pamphlet P-1, Safe handling of Compressed Gases in Containers NFPA 50 Standard for Bulk Oxygen Systems at Consumer Sites NFPA 55, Standard for the Storage, Use and Handling of Compressed Gases and Cryogenic Fluids in Portable and Stationary Containers, Cylinders and Tanks OSHA 29 CFR 1910.104: Oxygen; Bulk Oxygen Systems; Distance between Systems and Exposures; Fire Resistive Structures GSFC 23-81, Cryogenic Systems Hazards Analysis Checklist

GSFC 23-82, Dewar Personnel Certification

GSFC 23-81 Cryogenic Systems Hazards Analysis Checklists

GSFC 23-82 Dewar Personnel Training Records WFF NASA Ground Safety Plan and the Ground Safety Data Package WFF OSS Checklist for Operation- Cryogenics 803-OSSCL-CR (Attachment 1)

Acronyms
COTS Commercial Off the Shelf CSE Cryogenic Safety Engineer CSC Cryogenic Safety Committee GHe Gaseous Helium GN2 Gaseous Nitrogen GSC Goddard Safety Council GSFC Goddard Space Flight Center LHe Liquid Helium LN2 Liquid Nitrogen LO2 Liquid Oxygen NARA National Archive and Records Administration NRRS NASA Records Retention Schedule ODH Oxygen Deficiency Hazard OHO Occupational Health Officer OJT On the Job Training OSHA Occupational Safety and Health Administration PPE Personal Protective Equipment RECERT Recertification Program S&MA Safety and Mission Assurance Commonly used cryogenic fluids include the following: Liquid helium (LHe) normal boiling point 452F Liquid hydrogen (LH2) normal boiling point 423F Liquid nitrogen (LN2) normal boiling point 320F Liquid oxygen (LO2) normal boiling point 297F Liquid air (Lair) normal boiling point 318F Liquid argon (LAr) normal boiling point 303F

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In the handling of cryogenic liquids and the operation of low temperature facilities you have to consider two main risks. Cold Burns Asphyxiation- caused by the evaporation of cryogenic liquids in closed or badly ventilated areas Cryogenic fluids could cause any of the following safety problems: Asphyxiation Cryogenic burns from the extreme cold, eye damage from cold vapors. Skin stuck to cold surfaces. Over-pressurization and rupture of a pressure system or vessel--when cryogenic fluids try to vaporize due to heating from the surroundings, they can increase the pressure 650 to 1400 times.

Oxygen Enrichment
Upper respiratory irritation from breathing cold vapors. Fire and explosion. Leaks, sprays, or spills contacting nearby equipment and causing structural failures due to excessive thermal stresses within the materials.

Ice Buildup Ice Plugs

Direct contact with cryogenic liquids and gases as well as surfaces at cryogenic temperatures can lead to massive damages of the skin ( cold burns) or even of tissues, severe injury, and/or frostbite. The danger of cold burns is most prominent when handling open cryogen containers (LN2) Eyes and mucuous membranes are most at risk Cold conact burns. Liquid or low-temperature gas from any of the specified cryogenic substances will produce effects on the skin similar to a burn. Means of protection and preventive measures: Safety garments which prevent the penetration of cryogenic liquids (also see MSDS): eye protection gloves of insulating and non-combustible material, which can be easily be removed trousers without turn-ups which overlap the shoes Means of protection and preventive measures: Sufficient ventilation of the working place feed exhaust from transport dewars and from experiments into a gas recovery system or into the chimney equip working place with oxygen monitor enter confined areas, e.g. pits or tanks, only under supervision and only with portable oxygen monitors.

Oxygen Enrichment: At temperatures less than 82 K, metal surfaces will condense oxygen and form enriched air which can drip and form pools Liquefied air enriches to 50% O2
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Nitrogen, which has a lower boiling point than oxygen, will evaporate first, leaving an oxygen enriched condensate on the surface These surface will readily ignite and support combustion What you can do Insulate lines whenever possible, use heaters, use drip pans No smoking, open flames, ignition sources Try to eliminate combustible material in the vicinity of cryogenic systems

Liquid Air Hazards: Inadvertent contact with personnel Ex: WSTF technician and overhead, un-insulated LH2 vent line Inadvertent contact with unintended materials Embrittlement, contraction Combustion Shock sensitivity (e.g., asphalt)
Control Measures to Mitigate Hazards Associated with Cryogens Engineering Controls Pressure Relief Valves Insulation Ventilation Administrative Controls Training PPE (safety glasses, closedtoe shoes) Cryogen Handling Hazards. Asphyxiation (oxygen deficiency): Degrees of asphyxia will occur when the oxygen content of the working environment is less than 20.9% by volume. Effects from oxygen deficiency become noticeable at levels below ~18% and sudden death may occur at ~6% oxygen content by volume. This decrease in oxygen content can be caused by a failure/leak of the cryogenic vessel or transfer line and subsequent vaporization of the cryogen. The evaporation of cryogenic liquids in closed or badly ventilated areas can lead to oxygen deficiency Due to the fact that most cryogens are odourless and colourless, this hazard cannot be detected without special equipment The victim may not even become aware of the oxygen deficiency !!! Furthermore, argon and cold nitrogen are heavier than air and can therefore collect near the floor or in pits

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The symptoms of oxygen deficiency are ( oxygen concentration in % ): 19% - 15% 15% - 12% 12% - 10% 10% - 8% 8% - 6% 4% Pronounced reduction of reaction speed Deep breaths, fast pulse, co-ordination difficulties Vertigo,false judgement, lips slightly blue Nausea, vomiting, unconsciousness Death within 8 minutes, from 4-8 minutes brain damages Coma within 40 seconds, no breathing, death

Example for Helium: formation of fog !!! 100 x VO VR VO = 0.209 (VR VG) for cryogens other than oxygen VR is the volume of the room VG is the maximum gas release upon the expansion of the cryogenic liquid VR = 10 x 8 x 3 = 240 m3 VG = 710 x 0.05 m3 = 35.5 m3 (1 m3 = 1000 liters) VO = 0.209 (VR VG) = 0.209 (240 35.5) = 42.7 m3 Oxygen Content = (100 x 42.7)/240 = 17.8% To calculate the oxygen concentration when oxygen is the spilled cryogenic liquid, then VO = 0.209 (VR VG) + VG. Lighter or Heavier Than Air Lighter Heavier Lighter Heavier

Gas Helium Nitrogen Argon Hydrogen

Temperature Any Cold Warm Any Any

Monitor Placement Ceiling Floor Ceiling Floor

Table 6.1. Oxygen Monitors Placement

Implementing ODH Control Measures:

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Applicability This information applies to all staff where ODH classification of 0 or greater has been established. This information does not apply to Confined Spaces or when staff can be exposed to oxygen concentrations less that 19.5% under normal operations. Required Procedure The NASA GSG /Mission Manager or OSS if the affected area requires an ODH Classification. If the area is classified as ODH 0 or greater, then the following controls, based on classification, are as a minimum required to be implemented. Step 1 Based on the minimum oxygen concentration, the NASA GSG /Mission Manager or OSS and maintains the minimum controls required as follows: Oxygen Concentration 14% 10%<14% Controls Controls Required by ODH Classification (step 2). Controls Required by ODH Classification (step 2) plus ODH Monitoring (either fixed area or POM) that alarms locally. Controls Required by ODH Classification (step 2) plus ODH Monitoring that provides alarms/indication both locally and before entering the area.

<10%

Alarms must be perceptible in the environment used (e.g., visual or vibration in high noise areas). Note: Ensure to incorporate the impact from added monitoring to the ODH Classification process.

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Step 2

Based on the ODH Classification, the NASA GSG establishes and Mission Manager and/or OSS maintains the minimum controls required as follows: ODH Classification 0 Postings Training Postings Training (including practical demonstration of personal protective equipment [PPE]) PPE:
Personal Oxygen Monitor Self-Rescue Respirator (Supplied Atmosphere)

Controls

Ventilation Multiple Personnel in Communication (2-Staff Rule) Postings Training (including practical demonstration of PPE) PPE:
Personal Oxygen Monitor Self-Rescue Respirator (Supplied Atmosphere)

Ventilation Unexposed Safety Monitor/Observer Postings Training (including practical demonstration of PPE) PPE:
Personal Oxygen Monitor Self-Rescue Respirator (Supplied Atmosphere)

Ventilation Unexposed Safety Monitor/Observer Postings Training (including practical demonstration of PPE) PPE:
Personal Oxygen Monitor

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 Self-Contained Breathing Apparatus (SCBA)

Step 3

The NASA GSG /Mission Manager or OSS ensures that for staff authorized to work in areas classified as ODH-1 or higher; the staffs Occupational Medicine Clinic (OMC) Job Assessment Form (JAF) is annotated for potential ODH exposure. OMC will use specific surveillance protocols to determine if there are any potential medical issues that could restrict personnel from working in these areas. For personnel touring (not working in) an ODH Classified Area, see the section Escorted Access into ODH Areas for requirements. Note: Based on the OSHA Standard Interpretation: xx/xx/xxxx - Medical evaluation not required for the use of escape only respirators, the respirator surveillance sections of 29CFR1910.134(e) for use of Self-Rescue Respirator (supplying less than 30-minutes of breathing air) is not required. The use of Self-Contained Breathing Apparatus (SCBA) requires medical approval (including the respirator surveillance) from the OMC.

Step 4

The NASA GSG /Mission Manager or OSS ensures controls are implemented, including any monitoring/maintenance (i.e., calibration/replacement) requirements.

Protection Measures: Evacuation of the area Use safety garments: Always wear thermal protective clothing when handling refrigerated/cryogenic liquids or solids. It is required you wear a full face shield over safety glasses, loose fitting gauntlet gloves, long sleeve shirts, full-length trousers without cuffs, and fully enclosed shoes Control and measure O2 content of surrounding air Use independent breathing apparatus if needed Note: Helium (He): Is most dangerous area is on top Note: Cold N2 or Argon: most dangerous at the bottom Note: Vacuum flasks are at risk of implosion hazard and glass vessels under vacuum in particular may shatter unexpectedly. Chips, scratches or cracks can be a starting point for dangerous vessel failure, especially when the vessel temperature changes rapidly (when hot or cold liquid is added). Proper preparation of the Dewar vacuum flask by tempering prior to use is advised to maintain and optimize the functioning of the unit. Glass vacuum flasks are usually fitted into a metal base with the cylinder 20130408 8

contained in or coated with mesh, aluminum or plastic to aid in handling, protect from physical damage and to contain fragments should they break. Note: Cryogenic storage dewars are usually pressurized and may explode if pressure relief valves are not used.

Pressurization: All closed Dewars have some heat leak and will slowly build up in pressure over time A liquid helium dewar operating at 2 psig can pressurize to 12,000 psi if allowed to warm to room temperature without venting Relief valves protect dewars from over pressurization All dewars vent. Some occasionally, some constantly Soft vacuum raises pressurization rate Rapid Pressurization Full loss of insulating vacuum will result in rapid boil off of cryogen Quenching a superconducting magnet
Explosion Pressure: Heat flux into the cryogen from the environment will vaporize the liquid and potentially cause pressure buildup in cryogenic containment vessels and transfer lines. Adequate pressure relief must be provided to all parts of a system to permit this routine outgassing and prevent explosion. Explosion Chemical: Cryogenic fluids with a boiling point below that of liquid oxygen are able to condense oxygen from the atmosphere. Repeated replenishment of the system can thereby cause oxygen to accumulate as an unwanted contaminant. Similar oxygen enrichment may occur where condensed air accumulates on the exterior of cryogenic piping. Violent reactions, e.g. rapid combustion or explosion, may occur if the materials which make

contact with the oxygen are combustible.

Uninsulated surfaces will quickly ice up:

Valves can freeze inoperable 20130408 9

Vents can clog Wet rag leak stop

Staff and Administrative Responsibility: It is the responsibility of the experimenter in charge of an apparatus to ensure that the cryogenic safety hazards are reduced to as low a level as is reasonably achievable. This will entail (1) a safety analysis and review for all cryogenic facilities, (2) cryogenic safety and operational training for relevant personnel, (3) upkeep of appropriate maintenance and inspection schedules and records. It is emphasized that it is the responsibility of the experimenter to maintain the system in the original working order, i.e. the condition in which the system was approved for use. Alterations to the system which impact worker safety must be reported to the S&MA, NASA GSG, and the Navy at WSMR. The ultimate responsibility for safety rests with the worker and is best ensured by thorough education and awareness. Precautions To Observe When Working With Any Cryogenic Fluids If you handle any cryogenic fluids, you shall observe these precautions: Do tasks involving cryogenic fluids with two or more people, except for laboratory use from a small close container. Deactivate systems with proper energy controls found in NSROC Lockout/tagout procedure before you start any maintenance or repair work. Vent cryogenic systems through appropriate valves. Release gases so that the wind or room ventilation will direct them away from people. If you need to put warm objects in cryogenic fluids, do it slowly and use tongs to insert or remove the objects. If you need to put a cryogenic fluid into a warm container, do it slowly to minimize boiling, splashing, and thermal stresses. Keep unprotected body parts away from the cold surfaces of pipes or vessels that contain cryogenic fluids. Leave frost that forms on un-insulated surfaces undisturbed to help prevent Lair (LN2 plus LO2) from accumulating. Do a written hazard analysis for any area where cryogenic fluids are used or stored. Make sure you have a procedure or Standard Operating Procedure, and the GSP, GSDP, or RAR Ensure that all personnel involved are trained in the safe handling of cryogenic fluids.

Any work that you do with cryogenic fluids shall be: Near safety and firefighting equipment that you properly maintain. Away from combustibles. Away from unprotected or unauthorized personnel. In well-ventilated areas. Use oxygen analyzers and alarms to monitor for low oxygen concentrations, as required by the hazard analysis, if you are working with LHe, LH2, LN2, or LAr. Use oxygen analyzers and alarms to monitor for high oxygen concentrations if you are working with LO2. 20130408 10

Three types of containers. Dewar, Cryogenic Liquid Cylinder, and Cryogenic Storage Tank Storage varies from a few liters to thousands. Vaporization is always continuous. This is because heat leaks are always present. Know your specific container and proper handling procedures. Container Requirements: Closed container with a loose fitting top that allows venting. Use only vessels designed for extreme cold (i.e. insulated). Vessel must have carrying handles or be on wheels.

Potential Hazards Explosion: Liquid Nitrogen must be transported and stored in an appropriate container containing pressure relief devices. Otherwise, when the pressure builds up, o the stopper could be "rocketed out" o or worse, the container could explode Inappropriate Containers: DO NOT use open, un-insulated or glass containers! Insulating Vacuum:

Most cryogenic Dewars have vacuum shell surrounding the cryogen storage to minimize heat input Heat load is very sensitive to insulating vacuum Sweat (condensation) or frost buildup on a dewar is a likely indication of poor vacuum Frost is not unusual on some high pressure dewars Catastrophic loss of insulating vacuum will result in rapid release of cryogen Loss of vacuum is often the defining factor in sizing relief devices Insulating vacuum surrounding cryogens can pressurize on warm-up as any gas that may have leaked into the vacuum space expands These spaces must have over pressure protection as well Air leakage into vacuum insulation spaces surrounding a cryogenic vessel or line will condense to liquid (or solid depending on cryogen) Liquid has low vapor pressure masking size of leak Solid condensate gives no indication of presence (effectively no vapor pressure) Upon rewarming, gas expansion can crush inner vessel or rupture vacuum jacket Ice buildup on uninsulated areas can cause damage to surrounding equipment Potentially embrittle sensitive materials Adds additional weight to supports Can block relief valves or access to critical valves Freeze o-rings and compromise insulating vacuums
What will help: Insulate lines whenever possible 20130408

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Heaters Extending relief valves away from cold lines

Appropriate Containers: Examples of acceptable cryogenic Dewar's:

Safe

Handling: Wear Personal Protective Equipment: Face Guard, and Gloves Always use liquid Nitrogen in a well ventilated area. Use a loose-fitting stopper or lid that allows venting of the boil off. If using a funnel, use caution not to overfill the container. Only transport liquid nitrogen in the freight elevator with no occupants present inside; have one person on the delivery floor and another person on the destination floor, post sign on Dewar WARNING personnel not to enter. Only use containers that have been designed specifically for cryogenic liquids. Do not store in a confined space. Do not store at temperatures above 125F. Dewars Insulated, vacuum jacketed pressure vessels. Operate up to 350 psi and have capacities between 80-450 L. Product may be withdrawn as a gas by passing through an internal vaporizer. Or as a liquid under its own vapor pressure. Come equipped with safety relief valves and rupture discs. This protects from pressure build up. If there is any difficulty in the operating the container valve or connections discontinue use and contact the vendor. Do not remove or interchange connections. Use only the properly assigned connections. DO NOT USE ADAPTERS!

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Portable Nitrogen Dewar Operations:

There are two general types of portable liquid nitrogen dewars: - Low Pressure-For dispensing of liquid only. Relief valves set at 22 psig Burst disk set at 176 psig - High Pressure-For dispensing of liquid and gas. Pressure relief valve typically set at 230 psig or above. Always check the pressure gauge to determine the type of container before use High pressure dewars have an additional valve labeled gas and a pressure regulator equipped with a high pressure relief valve Avoid using high pressure dewars for low pressure applications if possible All potential trapped cold volumes must be protected by a relief device Trapped can be isolated by closing valves ASME Code: 1 relief device set at or below the maximum allowable working pressure (MAWP) Can have multiple devices, but all must be sized to handle full flow Rechecked periodically as per NASA directive (RECERT) NASA Governing Documents NPD 89710.5 NASA-STD-8719.17 GPR 8710.3 ASME certified relief valves can only be adjusted by certified personnel
Hearing a slight hiss from a liquid cylinder is usually the normal operation of its pressure relief device. Liquid cylinders should always be stored and used in areas with appropriate natural or mechanical ventilation. Never adjust, block, plug or attempt to repair anything on a liquid cylinder.

Pressure Relief Devices

Typical Direct Spring Loaded RV right angle 20130408 14

In-line relief valve

In-line relief valve

Relief devices must operate at room temperature and with cryogenic medium If proximity too cold equipment causes frost buildup on the relief valve it must be relocated Leaking relief valves that are building up frost must be repaired or replaced Never plug, restrict, or remove any relief device Unless as part of an approved procedure Never attempt to cap or seal a venting relief device in any way Do not tamper with, disable or adjust relief valve settings without proper review Even changing vent piping downstream of a relief valve can affect valve relieving capacity Stay clear of vent paths whenever possible

Pressure Relief Device Formula 4L 292 = 350 safety 4L 200 = 235 safety Pressure relief devices are prescribed based on the following formula for vacuum-insulated cylinders. (Cylinder service pressure X 1.25) 15psi = Maximum Pressure Relief Device Rating. o Example (200x1.25) 15psi = 235psi

Rupture Disks Non recloseable pressure relieving device Same capacity requirements as relief valves Disadvantage: Leaves system open to contamination after event Requires warm-up and purge to replace Subject to fatigue Relief at lower then design pressure (forward acting) Sensitive to installation Special holders required Torque to specified valves ASME code allows for rupture disks to be the sole over pressure protection device
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Liquid-to-Gas Conversion Liquid is converted to gas at about 2.3% per day even under ideal container conditions. If the liquid is not used regularly, the vessel will be empty in a certain amount of time. Cryogenic Liquid Containers (Liquid Cylinders) Always check the type of container that is being delivered or before use. One lab had ordered low pressure and received high pressure by mistake. The lab personnel assumed it was low pressure and began to use it. This could have resulted in an unsafe condition. Low pressure has an operating pressure of 22 psig!!! High pressure operates at 230 psig or above. Always check the pressure gauge to determine the type of container. Transfer Lines. Transfer lines are used to remove liquid from Dewar or cryogenic liquid storage containers. Cryogenic lines are always connected to the cylinders liquid withdrawal valve. A typical Dewar transfer line is connected to a bayonet. - This provides a means to remove product by pressure build up. Use only transfer lines designed for cryogenic equipment. Content Gauge on Liquid Cylinders The container contents gauge is a float-type liquid level sensor that indicates the level of the liquid. The gauge is an indication of approximate container content, and should not be used for judging the weight of the container. Containers are always filled by Weight Make sure you know the type of container that is used by your lab!! Low pressure is used only for the delivery of LIQUID, not gas Its operating pressure is 22 psig 20130408 16

 Caution Signs should be posted in the area warning that liquid nitrogen is being stored and used. Head pressure Results when heat leaks into the container The safety valve will periodically release this pressure If the safety valve malfunctions, a backup disk will rupture and relieve the pressure The rupture of the backup disk will produce a loud sound and may release a large quantity of liquid and gas. Evacuation of the area is required to prevent asphyxiation

Low Pressure Liquid Container Components Liquid Withdrawal Valve o Liquid is withdrawn through this valve Pressure Gauge o Displays internal pressure of the container Contents Gauge o A float-type liquid level gauge-indicates approximate level of liquid Vent Valve: Primarily used in the fill process to vent the vapor space while filling. Can be used to vent unwanted pressure during storage and use Pressure Relief Devices (2): Protect vessel from over-pressurization Re-seating spring-loaded relief valve releases at 22 psig Burst disk rated to protect the inner vessel Outlet Restraints

These are to prevent the dangerous practice of changing outlet connections at user sites. These restraints may be twist ties, wire, or other. Removal of these restraints will void all product warranties!! Kellum Grips, Lewis Grips attached to secure the hoses at both ends. Changing outlet connections is an extremely dangerous practice and can result in serious injury or death if an incompatible product is introduced into a users system. Never plug, restrict, or remove any relief device. Never attempt to cap or seal a venting relief device in any way. Ice or frost buildup on a pressure relief valve can be removed with a damp cloth. (Wear proper Personal Protective Equipment (PPE) when removing the frost.)
Transfer and Use: Use fitted transfer tubes designed for use with the dewar container. Damaged transfer tubes should be replaced. Do not handle transfer tubes with bare hands as the fitting in not insulated. When transferring into a secondary container, do not fill the secondary container to more than 80% of capacity (60% if the temperature is likely to be above 30 oC). Do not lower experiments into storage dewars unless provisions have been made to vent the dewar and prevent freezing in the narrow neck. 20130408 17

Immediately re-cap any container to prevent atmospheric moisture from entering and forming an ice plug. Use care in transporting fragile cryogenics containers. Use a hand truck for transport. Always transport cryogenics liquids in service elevators when available. Use only approved storage vessels having certified pressure relief valves. Industry practice do not normally certified there relief valves, but NASA does. Periodically check containers to prevent ice plugging of the relief devices. a. Do not directly touch or make contact with cryogenic liquids or uninsulated cryogenic equipment or pipes. Tongs can be used to withdraw objects immersed in a cryogenic liquid. b. Do not overfill containers. In addition, when pouring or transferring cryogens, one must do so slowly to minimize boiling and splashing. c. Avoid the path of boil-off gases. d. Ensure that cryogenic fluids are stored in appropriately insulated containers which minimize the loss of product due to boil-off. (Dewar flasks are commonly used.) e. Containers of cryogenic liquid must never be closed so that they cannot vent. Where a special vented stopper or venting tube is used, as on some small portable containers, the vent must be checked regularly to ensure it has not plugged with ice formed from water vapor condensed from the air. (1) Ordinary glassware must not be used to store or transfer cryogenic liquids. All unprotected glass Dewar must be wrapped with a heavy adhesive tape to prevent fragmentation and to provide a better gripping surface. The materials used in cryogenic systems must have the appropriate physical properties to qualify them for use at these extremely low temperatures. Some acceptable materials are: (a) Aluminum (b) Series 300 Stainless steels (such as 304, 316) (c) Copper (d) Brass (e) Fiberglass (i.e., G-10) (2) Materials susceptible to hydrogen attack and hydrogen embrittlement must NOT be used in hydrogen service. Avoid the following materials: (a) Titanium (b) Maraging steels (c) SA-517 (or similar heat-treated steels (d) Series 400 Stainless steels 20130408 18

(e) MIL-S-16216 and (f) Precipitation-hardened stainless steels. f. All system vents must be directed away from personnel or designated work areas. Venting fluids (liquids or cold gases) should not impinge on any part of the body of either the worker or other personnel. g. Pressure may build-up in liquid Nitrogen storage cylinders. Ensure all safety valves and vent valves are unobstructed and functioning properly. Check the safety vents on liquid nitrogen tanks at least twice a week. h. Inspect and maintain cryogenic systems and equipment on a regular basis. l. Ensure that appropriate personal protective equipment is worn when working with cryogens. High-pressure gas: Working with or storing cryogenic fluids presents hazards from high-pressure gas, since the liquefied gases are usually stored at or near their boiling points, and therefore there is always some gas present in the container. Due to the large expansion ratio from liquid to gas, a buildup of high pressure can occur when the liquid evaporates. The evaporation rate will depend on the fluid, storage container design and environmental conditions, but the container capacity must include an allowance for the evaporation of the liquid into the gaseous state. To prevent hazards associated with high-pressure gas, it is important to ensure that pressure relief devices are used appropriately. These devices should be maintained and checked regularly for leaks or damage. Pressure relief devices must be sized for maximum possible back pressure. All venting should be controlled, and free venting of any cryogen should be eliminated or tightly controlled.

Standard Operating Procedure (SOP) for the filling of 25L liquid nitrogen belly dewars from
the 250L liquid nitrogen vessels: Please note: Only researchers trained may fill 25L belly dewars. This task must be done in pairs. Wheel the belly dewar beside the 250L vessel. Ensure you are wearing a lab coat, face shield and thermally insulating gloves. Remove the cap from the belly dewar . Carefully insert the transfer line from the 250L vessel into the belly dewar. Slowly turn the tap labelled LIQUID FILL/DECANT with the transfer line attached. (see photographed below) Fill the belly dewar to approximately 90%. Close the tap labelled LIQUID FILL/DECANT firmly. Carefully remove the transfer line from the belly dewar and rest it against the 250L vessel. Place the cap back on the belly dewar. Inform a Stores Officer you are finished.

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Transport. Find a cart Dont try to carry or roll the container. Keep upright Dont try to pull the container, always push. Avoid mechanical or thermal shock. Sudden environmental change could potentially change the pressure. Gas Withdrawal. Connect a control regulator to the gas withdrawal valve and the outlet of the valve to the system receiving gas. Open withdrawal and pressure building valves until the container reaches desire pressure. You may begin withdrawing gas. Liquid Withdrawal. Always wear a face mask for liquid withdrawal. Connect a transfer line from the liquid valve to the system being filled. Open valve to desired rate of flow, close when finished. To prevent back contamination, all valves should be closed when the container has been emptied.

Transferring 20130408 20

Precautions For Transferring Cryogenic Fluids If you transfer, use, or store any cryogenic fluids, you shall observe these precautions: Transfer liquid slowly to reduce thermal shock to containers. Dont breathe cryogenic vapors. Dont allow ice to accumulate on a neck of or near the vent of a cryogenic vessel. Ice could plug the vent and cause the vessel to rupture. Empty and purge any cryogenic vessel with ice accumulating on the outer surface and either dispose of it or take it out of service for repair. The ice indicates a poor vacuum in the annular space resulting in poor insulation. Tape or cage exposed portions of glass containers to minimize flying glass if the glass breaks. Follow these requirements to prevent sparks or arcs: Ground all stationary hydrogen and oxygen equipment. Bond mobile and stationary equipment used to transfer and receive Lair, LO2, and LH2 and make sure that all equipment involved in the transfer shares a common ground. Purge all condensable gases from LH2 transfer hoses in service with helium gas. Transfer LH2 only with specially designed equipment. Nitrogen (GN2) Do: use a metal line wear safety glasses, face shield and apron Helium (He) Do: open relief valve when finished, close other valves. wear safety glasses, face shield, apron and proper shoes. vent dewar and cryostat before transferring Pressurize with dry He gas. Dont: forget to tighten fill port on cryostat when done mistreat delicate transfer lines Pressurize more than 8 psi Stand in vapor cloud. Dont: use a latex line Wear opentoe shoes

See video on Sample Environment website for more instruction How to refill Liquid Helium. http://www.ncnr.nist.gov/equipment/ancequip.html

Warning signs of a damaged dewar or cryostat: Continuous venting from a vent valve is not normal. It could mean there is dirt in the vent 20130408 21

valve or it is damaged. Sweat or Frost at the bottom or sides of a dewar or cryostat is an indication of a faulty or damaged vacuum jacket. If you discover a dewar or cryostat in this state, at WSMR contact the Navy or the manufacture.

Pressure build-up. Independent pressure relief devices for each component that can be isolated by valves and each closed space Keep valves closed on LHe dewar to prevent creation of ice plugs Only pressurize LHe dewars with He!

Storage
Locations where cryogenic fluids are stored shall follow these requirements: Keep in a well ventilated room The room shouldnt be a confined area to help exhaust any nitrogen gas off-gassing from the container. A non ventilated room could very quickly become oxygen deficient. It is also recommended that the building that the nitrogen is stored in has an exhaust ventilation system to outside the building. All labs should have this system installed. Do not leave Dewar containers uncovered, but make sure to have an exhaust system If the container is completely covered, the pressure could increase to dangerous levels, so exhaust is required. If left completely uncovered, the liquid nitrogen will evaporate much faster. Store in a controlled environment Away from weather change. This will help the nitrogen from undergoing drastic changes in temperature or pressure. Store cryogenic fluids outside or in large, open, and well-ventilated rooms that are vented to the outside. Use oxygen analyzers and alarms. Continuously ventilate any area where inert cryogenic fluids are used, even at night and on weekends, unless you remove them from the area. Leave air handlers or exhaust ventilation on at all times. Label the entrance to any area with inert cryogenic fluids to alert personnel that asphyxiation is possible in that area due to oxygen-displacing cryogenics. If you store LH2 inside, make sure to vent any gas that escapes either to the outside or to a safe location. If you vent the gas through ductwork, the ductwork shall be independent of other systems and contain no ignition sources. You shall use hydrogen detectors (either permanently installed or portable) wherever you use hydrogen. Within 3 feet of hydrogen sources (such as where connections are regularly made and disconnected), you shall use Class I, Division 1, Group B electrical equipment as described in National Fire Protection Association Standard 70, National Electric Code. Between 3 and 25 feet of hydrogen sources, you shall use Class I, Division 2, Group B electrical equipment. 20130408 22

Storage in Cold Rooms Ice Plugs Frozen plugs can form in dewar plumbing if the cryogenic system is exposed to air Moisture in air can also block lines The smaller the vent line the more susceptible to plugging Sometimes fill or vent lines are also the path to relief valves Plugs in these lines could potentially prevent the vent valves, as well as pressure relief valves, from releasing pressure from the Dewars as the cryogen vaporizes Over time this will result in a pressure buildup that can cause structural failure of the Dewar WAYS TO AVOID THIS Minimize exposure of any cryogenic system to air Any valves that lead to ambient should be kept closed as much as possible and only be opened when required by procedure Purge transfer line prior to inserting it into cold dewar Use check valves or extended length tubes on vents normally open to air SOLUTION Warm (room temperature) blunt copper rod Contrary to popular belief, storage of liquid containers in cold rooms will not slow down the liquid to gas conversion. Storage in cold rooms can create an oxygen deficient atmosphere if the room does not have adequate ventilation to remove the nitrogen gas generated.

Removing an ice plug. First, ice plugs can kill you. If someone is attempting to remove an ice plug: Ice or frost buildup on a pressure relief valve can be removed with a damp cloth. (Wear proper Personal Protective Equipment (PPE) when removing the frost.) Helium (He) ice plug removal only: Direct a flow of room temperature He gas (not any other gas!) onto the plug Find a suitable length Copper rod, affix a stop point so it does not drop all the way into the dewar, contact ice plug. Only use this technique if there is little pressure build-up

You must take all precautions to prevent air having any chance to get inside a cryostat or Dewar.

Water in the air can freeze and form a block inside the neck at a point where the temperature is 0 oC, trapping liquified air below it. 20130408 23

When this liquefied air boils, pressure builds (remember our expansion ratio of ~700?) it can cause the stick to be forcefully ejected, or in extreme cases can cause the dewar or cryostat to explode. You must NEVER allow any part of your body to be directly over the sample stick in any kind of cryostat. Ways to cause an explosion: By sealing any pressure relief valves on a cryogenic system or dewar. By leaving a LHe or LH2 dewar transfer valve open such that as the initial boil off decreases, air can get into the dewar and freeze solid, resulting in a plug inside the dewar. This prevents the pressure relief valves from working, resulting in a slow build up of pressure! Maximum Pressures of Filled Vessel Warming to 300K without Venting

Explosion caused by improper venting or accidental rapid warming of evaporating cryogen is the single biggest safety hazard. This is because the cryogenic liquids have a much higher density than their gases at room temperature. Cryogen Helium Hydrogen Nitrogen Maximum Pressure (Mpa) (psi) 103 (15,000) 172 (25,000) 296 (43,000)

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Training To Work With Cryogenic Fluids Your training shall cover the following subjects for each cryogenic material you work with: Nature and properties of the cryogenic fluid in both liquid and gaseous states. Correct personal protective equipment (PPE) to use in specific environments and where you can find it. Approved materials that are compatible with the cryogenic fluid. Proper use and care of protective clothing and equipment. First-aid procedures. Emergency procedures for handling situations such as leaks, spills, and fires. Good housekeeping practices.

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Sources of Accidents and Failures Embrittlement.

Low temperature embrittlement: Causes overloaded components to fracture spontaneously rather than accommodating the stress by plastic deformation Appropriate steels for low temperature use are listed in the Technical Rules for Pressure Vessels AD-Merkblatt W10 . In general, materials with face-centered cubic (fcc) crystal structure as copper, nickel, certain copper nickel alloys, zircon and titanium are suitable for cryogenic applications. If hydrogen is present during the production of materials or if components come into contact with hydrogen in operation, then hydrogen embrittlement can occur under certain conditions. Sources of Accidents and Failures. Thermal Stress: The development of thermal stress is due to the contraction of materials when cooled down to cryogenic temperatures. The stress can appear as a transient effect e.g. when cooling down thick walled components or it can appear as permanent load e.g. in piping. In both cases the stress can cause damage. As the expansion coefficient of most materials decreases with temperature, most contraction takes place above LN2 temperature ( 77K). Sources of Accidents and Failures Pressure Build-up by Evaporation: Cryogen liquids do expand by a factor of 500 to 1500 when evaporated and warmed up to room temperature (300 K); Helium: 2K l -> 300K d factor= 900 -> significant pressure build-up in a closed container Possible reasons for an elevated heat input are: fast cooldown of components or cryogenic installations, large heat production within the object to be cooled ( e.g. quench) , loss of insulating vacuum, thermoacoustic oscillations. Comparison (ideal) Gas: e.g. Helium T > 30K Pressure x Volume = const x Temperature at Pressure = CONST -> Volume = const/CONST x Temperature -> Double Temperatur ->Double Volume Further mechanisms which can lead to a pressure increase. Boiling retardation: In very clean vessels boiling may not start but at temperatures above the boiling point. In this case the boiling can be from violent to explosion like. Boiling retardation can be prevented by introducing porous material as boiling nuclei. Stratifikation: If the cryogen in a large tank is not disturbed for some time, a temperature stratification may occur. The stratification causes a larger pessure rise than expected due to the elevated temperature in the liquid surface layer.

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The Release of Cryopumped Gas Sources of Accidents and Failures Preventive Measures Against Pressure Build-up. Redundancy: i.e. more safety devices than required double safety devices Diversity: i.e. safety devices based on different mechanisms Sources of Accidents and Failures Condensation of Gases.

Purposeful use of condensation in cryo-pumps and cryotraps Danger: Freeze-up of exhaust pipes of dewars by air and/or air moisture. The plugging causes pressure buildup. Dewar pressurization, venting, and liquid extraction (Not liquid Helium) This schematic of typical vent system for a large liquidhyrdogen storage Dewar. (1) Dewar pressurization valve, (2) Fast vent valve; (3) normal boil-off control valve; (4) Safety relief valve; (5) rupture disk; (6) Gas pressurization/vent ring (holes on top side only help preserve thermal stratification and erduce liquid entrainment in vent gas); (7) Liquid discharge valve; (8) Pressure relief valve for annulus. Note: 7. Liquid extraction valve has a gas trap which prevents constant heat leak from the liquid exposed to the room temperature. Preventive Measures: Only use dewars with separated eshaust and safety valve lines Do not leave dewars open to atmosphere Equip exhaust lines to atmosphere with check valves ( nonreturn) Perform a leaktest before evacuating cryogen baths with emphasis on leaks by which air might be sucked into the cold part of the apparatus LN2 exhaust line: Danger of freeze-up Fill Hose: The liquid Nitrogen is released through this hose Procedures: Step 1: Fill Hose, insert and hold the fill hose into the appropriate container or into the funnel

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Step 2: Open/Close Valve Open valve slowly to begin filling. Close valve tightly after filling. Unwanted condensation or freezing can also lead to: - Mechanical damage By ice accretion on valves, turbines etc., By dripping condensate at cryogenic temperatures or By water condensate - Pressure build-up by desorption - Formation of explosive mixtures: By condensation of air or oxygen on combustible liquids or materials flammable up to explosive mixtures can be created: In the insulation material of transfer lines, in a liquid hydrogen dewar on the active charchoal of a cryogenic adsorber. Important ! Air condensate is a strong promoter of combustion as it can have an oxygen concentration of up to 50%. This is due to the higher boiling point of oxygen. Sources of Accidents and failures : Combustion and Explosion Hazard Oxygen

Liquid or gaseous oxygen can - strongly promote combustion processes, reduce the ignition temperature, accumulate in combustible materials ( especially also in clothes), which will burn from violent to explosion like when ignited. Ozone; A safety risk is posed by the production of ozone in systems which contain oxygen and which are exposed to gamma or neutron radiation. An explosive amount of ozone can already be created from the oxygen impurities in a liquid nitrogen dewar.

Preventive measures against condensation and its consequences: 20130408

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Purge and evacuate all equipment thoroughly before operation. Operate installations at slight overpressure in order to avoid impurities from entering through leaks. Whereever possible do use vacuum insulation. Otherways- do not use incombustible insulation material. Identify unsafe conditions and/or practices and assist in the development of corrective action plans. Review personnel accidents, near-misses, and recommend preventive measures.

General Safety Measures: Immediately call 9-1-1 emergency personnel in the event of a large spill or leak. Isolate large spills or leaks for at least 100 meters in all directions. -- Refer to both the MSDS and the Emergency Response Guide 2008 Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate closed spaces before entering. All work in cryogenic areas has to be checked an approved by NASA GSG, the OSS and the experimenter cryo-operators (PI) in charge Inform the NASA GSG, the OSS and the experimenter cryo-operators about any problems Follow the operating instructions Install oxygen monitors in areas were operations using cryogenics will be conducted and storage area where oxygen deficiency hazard (see Table 6.1. Oxygen Monitors Placement) with a level of risk greater than Class 0.

Other safety measures: If your skin comes into contact with liquid nitrogen may cause frostbite and burns. Seek immediate medical attention. Call 911 If liquid is splashed in the eyes, flush with water for at least 15 minutes. Seek immediate medical attention. Call 911 Skin contact is a medical emergency. Lack of prompt medical attention may result in amputation!!! CALL 911 In case of a lack of oxygen, move immediately to a well-ventilated area, or outside and acquire a respirator. Reentry may only occur by trained personnel with air supplying respirators. Determining Worst-Case Failure Modes: For each volume requiring a relief valve, a credible worst-case failure mode must be determined. Generally, one should consider for a given failure mode only a single initiating failure (of either a procedure or a component), together with any subsequent failure or chair of failures that would naturally result from the initial failure. The following are examples of failure modes that should be considered:

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A. An operator improperly opening or closing any given valve. This might result, for instance, in liquid nitrogen then being trapped in a section of transfer line, or in air being introduced into a cryogenic insulating vacuum. B. Failure of a cryogenic vacuum vessel to air. C. Failure of a vessel containing cryogenic liquid into the insulating vacuum vessel. D. Failure of the inner, cryogenic tube of a transfer line. E. Failure of the outer, vacuum housing of a transfer line. In case A, above, the effects of opening valves to or from any connecting systems, such as gas storage or refrigerator, should also be considered. For relief valve sizing, the worst-case failure mode is that failure mode resulting in the most rapid boil off of cryogenic fluid. With the exception of failure modes that cause the injection of cryogenic fluid from an outside system, the boil off will be determined by the heat-leak caused by the given failure mode. Some Heat Transfer Processes: Determination of the heat leak due to a given failure requires detailed analysis of the particular system. The general methods for several cases are outlined below.

Condensation of Air on Vessels Containing Liquid Helium: For a bare (not wrapped in super-insulation) cryogenic vessel containing liquid helium, the worst-case failure mode is likely to be failure of the insulating vacuum to air. All the constituent gases of air will condense directly on the surface of the helium containing vessel; from reference [1], p. 270, such condensation produces a heat input of 1 to 6 watts/cm 2. For the ATLAS cryostats, an experiment was performed to determine the precise number, which turned out to be 1.4 watts/cm 2. In the absence of such experimental data, the most pessimistic value, 6 watts/cm 2 should be assumed. The heat leak due to air condensation for vessels which are wrapped in super-insulation. Convective and Conductive Heat Transfer: In many cases the worst-case failure mode will be failure of an insulating vacuum to air, nitrogen, or helium with the heat transfer mechanism then being convection, or in the case of substantial amounts of super-insulation or other filler conduction, from the outer vacuum wall of the vessel to the inner vessel or piping containing the cryogenic fluid. The thermal conductivity of several gases. Determining Boiloff Rates: Once the heat input to the cryogenic substance is known, the maximum rate of efflux must be determined.

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In many cases the efflux results from simple boiling of a cryogenic fluid, and the rate can be simply estimated from the heat of vaporization of the cryogenic liquid. In general, the efflux must be calculated by equating the enthalpy released by venting a portion of the cryogen (at the relief pressure) to the worst-case heat input. This may or may not be a simple matter, depending on the conditions that apply. Determining Pressure Drop from Venting Vessel to Atmosphere: For most vent lines and valves, the pressure drop will be dominated by the so-called minor loss term, which is approximately

|P=1/2G2/
where G is the mass flow per unit cross-sectional area in grams/ (sec * cm2), and is the gas density at the exit of the element considered. Each bend or orifice in the flow path that causes substantial turbulence will add a term roughly given by expression (1) to the total pressure drop. Details the pressure drops expected for various geometries of bends and orifices. Expression (1) shows that for a given pressure drop, the flow through any system, such as a relief value, will scale as G2/. Since manufacturers specifications usually give capacity for air at room temperature, this scaling relationship provides a means of estimating capacity of a given valve for various gases at cryogenic temperatures, such as nitrogen at 77 K or helium at 5 K. Helium from 15 K to 77 K (Tf = 46 K, T = 26 K) kf = 4.52x10-4 W/cm K, f = 1.06x10-3, f = 60x10-6 poise, thus

RELIEF VENT PRESSURE DROPS We calculate the pressure drops caused by the flow of gas through tubes and orifices using (CGS units) the following: Define G = mass flow (grams/(sec.cm2)) = density (g/cm3) = viscosity (poise) For flow through a tube or channel 20130408 31

P=lG2(2Dn)

where cross section area Dn = effective diameter = 4 x section total perimeter = length of tube and = 0.326 (GDn/) -0.25 (turbulent flow) We also include a minor loss term 1 G2 P = 2 for the pressure drop occurring at any orifice or sharp bend in the flow channel. For most relief path geometries term (2) will be larger than term (1). Application of expression (2) is not always straightforward, a number of examples are discussed in ref. [8]. In what follows we assume the density of helium to scale according to the ideal gas law. Equipment Failure Rate Estimates Failure Mode Compressor (Cryogenic) Dewar Leak or Rupture Leak or Rupture Estimated Median Failure Rate 3 x 10-5/hr

1 x 10-6/hr 1 x 10-4/hr (1 hr) 3 x 10-6/hr 1 x 10-6/hr

1 x 10-3/hr 4 x 10-5/hr

Electrical Power Failure Time Rate (unplanned) (Time Off) Fluid Line Leak or Rupture (Cryogenic) Magnet Leak or Rupture (Cryogenic) Small Event U-Tube Change Release (Cryogenic) Large Event - Electronic reliability analysis MIL-STD-217F, and notice F1 and F2 - Mechanical reliability analysis NSWC 2011 and Parts Listing in NPRD 2011 NFPA 704 Labeling System for Chemicals

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Ensure you have a copy of the MSDS and know the hazards for the type of cryogenic. Hazardous Material Identification System Guide

Lockout/Tagout: Lockout/Tagout refers to specific practices and procedures to safeguard employees from the unexpected startup of machinery and equipment, or the release of hazardous energy during service or maintenance activities. Lockout/Tagout requires that a designated individual turns off and disconnects the machinery or equipment from its energy source(s) before performing service or maintenance. 20130408 33

Authorized employee(s) either lock or tag the energy-isolating device(s) to prevent the release of hazardous energy and take steps to verify that the energy has been isolated effectively. Lockout/Tagout devices should be removed by the individual who originally placed the lockout/tagout device. If the employee who applied the device is unavailable, it may only be removed after management has verified the employee is not available and has ensured it is safe to remove the device. Management must then make all reasonable efforts to contact the employee and inform them that the device has been removed.

Lab Safety Donts: Dont completely seal off the container. At room temperature, nitrogen is going to create a gas. This requires exhaust, or the container could potentially explode. Funnel the liquid nitrogen This could potentially cause spills and splashes that could come into contact with skin. Dip a hollow tube into the container could potentially splatter. Trouble Shooting Issue 1: Gas vents intermittently through safety relief valve Possible cause: Probably normal operation. Gas generated due to heat leak into cylinder causes head pressure to build Recommended Activity: Ensure inactive containers are stored in well-ventilated area. Rotate the inventory

Issue 2: Gas vents continuously through safety valve Possible Cause: Possible relief valve failure or excessive heat leak Recommended Activity: Remove container or vent the exhaust to a well-ventilated area. Relieve product through vent valve. Check to see if safety relief valve is frozen open. Contact supervisor or supplier for assistance Issue 3: Gas vents during use through safety relief valve Possible Cause: Set point on regulators exceeds safety relief valve setting Recommended Activity: Reduce set point on pressure building regulator-Contact supervisor or supplier for assistance

Issue 4: Pressure in the container is low Possible Cause: Leak from container Recommended Activity: Use appropriate leak detection fluid to check for leaks in connections. Examine container for signs of frost. If leaks are on container itself, contact supervisor or supplier

Issue 5: Pressure in the container is low Possible Cause: Pressure building valve is not fully opened Recommended Activity: Slowly open valve fully 20130408 34

 Issue 6: Pressure in the container is low Possible Cause: Pressure building regulator not set high enough Recommended Activity: Adjust to increase pressure-contact supervisor or supplier o o o Issue 7: Pressure in the container is low Possible Cause: Pressure building valve is open Recommended Activity: Close the valve if frost is visible on the pressure building vaporizer near the bottom of the tank-contact supervisor or supplier

Issue 8: Pressure in the container is too high Possible Cause: Leaking or improper setting of pressure building regulator Recommended Activity: Reduce regulator setting to achieve desired pressure level-contact supervisor or supplier Issue 9: Pressure in the container is too high Possible Cause: Vacuum integrity failing Recommended Activity: If container walls are covered with frost, contact supervisor or supplier Issue 10: Container top covered with frost Possible Cause: High product use Recommended Activity: Normal operation

Issue 11: Container has isolated spots of frost Possible Cause: Container may have been damaged, compromising integrity of insulation Recommended Activity: Contact supervisor or call supplier for replacement Issue 12: Container surface is uniformly covered with frost Possible Cause: Vacuum integrity compromised Recommended Activity: If accompanied by a high rate of product venting through the safety relief valve, or high rate of pressure increase, call supplier

Physical Properties of Gases As mentioned earlier, gases are compressible and, as such, knowledge of the pressure generated by a gas as it relates to temperature and volume are critical to any application from both a performance and safety perspective. 20130408 35

From a performance perspective, knowledge of the boiling point and freezing point may be relevant, but the auto-ignition temperature, the minimum temperature required to ignite a gas or vapor in air without a spark or flame present, is of paramount importance.

The flammable (or explosive) range is the range of a gas or vapor concentration that will burn or explode if an ignition source is introduced. Limiting concentrations are commonly called the lower explosive or flammable limit (LEL/LFL) and the upper explosive or flammable limit (UEL/UFL). Other properties that are relevant to particular applications include:

Specific Volume (ft3/lb., m3/kg) Density of liquid at atmospheric pressure (lb./ft. 3, kg/m3) Absolute Viscosity (lb.m/ft. s, centipoises) Specific Heat - cp - (Btu/lboF or cal/goC, J/kgK) Specific Heat Ratio - cp/cv Gas constant - R - (ft. lb./lboR, J/kgoC) Thermal Conductivity (Btu/hr. ft. oF, W/moC) Boiling Point - saturation pressure 14.7 psia and 760 mm Hg - (oF, oC) Latent Heat of Evaporation at boiling point (Btu/lb., J/kg) Freezing or Melting Point at 1 atm (oF, oC) Critical Temperature (oF, oC) Critical Pressure (psia, MN/m2) 20130408 36

Critical Volume (ft.3/lb., m3/kg)

Major Industrial Gases While there are literally thousands of available industrial gases, certain industrial gases are major elements of the world economy. Major gases include:

Hydrogen (H) - a colorless, highly flammable, gaseous element. It is used in the production of synthetic ammonia and methanol, in petroleum refining, in the hydrogenation of organic materials, as a reducing atmosphere, in oxyhydrogen torches, and in rocket fuels. Ordinary hydrogen gas is made of diatomic molecules (H2) that react with oxygen to form water (H2O) and hydrogen peroxide (H2O2), usually as a result of combustion.

Hydrogen Bromide - an irritating, colorless gas used in the manufacture of barbiturates and synthetic hormones. Hydrogen Chloride (HCl) - a highly corrosive and toxic, colorless gas. White fumes form on contact with humidity. HCl often refers to hydrochloric acid, which is actually a mixture of hydrogen chloride in water. Hydrogen Fluoride (HF) - a colorless, fuming, corrosive liquid or a highly soluble, corrosive gas used in the manufacture of hydrofluoric acid; as a reagent, catalyst, and fluorinating agent; and in the refining of uranium and the preparation of many fluorine compounds. Hydrogen Sulfide (H2Se) - a colorless, flammable, poisonous gas with a characteristic rottenegg odor. It is used as an antiseptic, bleach, or reagent.

Nitrogen - a nonmetallic element that constitutes nearly four-fifths of the air by volume. It occurs as a colorless, odorless, almost inert, diatomic gas (N2), in various minerals. Nitrogen is found in all proteins 20130408 37

and used in a wide variety of important manufactures, including ammonia, nitric acid, TNT, and fertilizers. Atomic number 7; atomic weight 14.0067; melting point -209.86C; boiling point -195.8C; valence 3, 5.

Ammonia (NH3) - toxic and corrosive to some materials; with a pungent odor. Ammonia is used in the production of fertilizers, explosives, polymers, and household cleaners Nitric Oxide (NO) - a toxic air pollutant produced by automobiles and power plants. Nitrous Oxide -include dinitrogen oxide (N2O, nitrous oxide), dinitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4), and dinitrogen pentoxide (N2O5). Nitrogen Dioxide (NO2) - a poisonous brown gas often found in smog and automobile exhaust fumes. It is synthesized for use as a nitrating agent, a catalyst, and an oxidizing agent. Nitrogen Trifluoride (NF3) - a colorless gas that has a melting point of -206.6C and a boiling point of -128.8C; used as an oxidizer for high-energy fuels.

Air - a colorless, odorless, tasteless, gaseous mixture; mainly nitrogen (approximately 78 percent) and oxygen (approximately 21 percent), with lesser amounts of argon, carbon dioxide, hydrogen, neon, helium, and other gases.

Oxygen (O2) - an atmospheric gas. The abundance of free oxygen is due to photosynthesis by plants. Carbon Dioxide (CO2) - a common chemical compound formed as a byproduct of respiration, fire, and combustion. Carbon Monoxide (CO) - a flammable, toxic, colorless, and odorless. It is also a major byproduct of combustion. Ethylene Oxide (CH2)2O - a colorless gas, soluble in organic solvents and miscible in water; boiling point 11C; used in organic synthesis for sterilizing, and fumigating. Also known as 1,2-epoxyethane epoxide; oxirane Sulfur Dioxide - sulfur dioxide (SO2) is a colorless, extremely irritating gas or liquid used in many industrial processes, especially the manufacture of sulfuric acid.

The Noble Gases:

Argon -one of the inert or noble gases. Argon gas is colorless, odorless, nontoxic, and nonflammable. Argon is typically shipped as a compressed gas. Helium - a colorless, odorless, inert, gaseous element occurring in natural gas and with radioactive ores. It is used as a component of artificial atmospheres and laser media, as a refrigerant, as a lifting gas for balloons, and as a superfluid in cryogenic research. Atomic number 2; atomic weight 4.0026; boiling point -268.9C; density at 0C 0.1785 gram per liter. Krypton - a whitish, largely inert, gaseous element used chiefly in gas discharge lamps and fluorescent lamps. Atomic number 36; atomic weight 83.80; melting point -156.6C; boiling point -152.30C; density 3.73 grams per liter (0C).

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Neon - a whitish, largely inert, gaseous element used chiefly in gas discharge lamps and fluorescent lamps. Atomic number 36; atomic weight 83.80; melting point -156.6C; boiling point -152.30C; density 3.73 grams per liter (0C). Xenon - a colorless, odorless, highly unreactive, gaseous element found in minute quantities in the atmosphere, extracted commercially from liquefied air and used in stroboscopic, bactericidal, and laser-pumping lamps. Atomic number 54; atomic weight 131.29; melting point -111.9C; boiling point -107.1C; density (gas) 5.887 grams per liter; specific gravity (liquid) 3.52 (-109C).

The Hydrocarbon Gases:

Acetylene - a colorless, highly flammable or explosive gas; C2H2 is used for metal welding and cutting and as an illuminant. Also called ethyne. Butane - two isomers of a gaseous hydrocarbon; C4H10 is produced synthetically from petroleum and is used as a household fuel, refrigerant, and aerosol propellant, and in the manufacture of synthetic rubber. Butadiene - a colorless, highly flammable hydrocarbon, C4H6 is obtained from petroleum and used in the manufacture of synthetic rubber. Butene - any of three isomeric hydrocarbons C4H8; all used in making synthetic rubbers; also known as butylene. Ethane - a colorless, odorless, gaseous alkane; C2H6 occurs as a constituent of natural gas and is used as a fuel and a refrigerant. Ethylene - A colorless flammable gas; C2H4 is derived from natural gas and petroleum, and is used as a source of many organic compounds: in welding and cutting metals, to coloring citrus fruits, and as an anesthetic. Also called ethene. Methane - an odorless, colorless, flammable gas; CH4, the major constituent of natural gas, is used as a fuel, and is an important source of hydrogen and a wide variety of organic compounds. Propane - A colorless gas, C3H8 is found in natural gas and petroleum, and is widely used as a fuel. Propylene - a flammable gas, CH3CH:CH2 is derived from petroleum hydrocarbon cracking and used in organic synthesis. Also called propene.

The Halogens:

Chlorine (Cl2) - a diatomic gas that is yellow-green in color. It is a halogen that combines easily with nearly all other elements. Chlorine irritates the respiratory system and mucous membranes. It is fatal in amounts of 1,000 ppm or more. Prolonged exposures at lower, nonfatal levels weaken the lungs. Boron Trichloride - A flammable gas, CH3CH:CH2 is derived from petroleum hydrocarbon cracking and used in organic synthesis. Also called propene. Chlorine Trifluoride (ClF3) - a colorless, poisonous, corrosive, and very reactive gas that condenses to a pale, greenish-yellow liquid -- the form in which it is most often sold 20130408

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(pressurized at room temperature). The compound is primarily of interest as a component in rocket fuels, in industrial cleaning and etching operations in the semiconductor industry, in nuclear reactor fuel processing, and other industrial operations

Dichlorosilane (H2SiCl2) - or DCS as it is commonly known, is usually mixed with ammonia (NH3) in LPCVD chambers to grow silicon nitride in semiconductor processing. Ethyl Chloride (C2H5Cl) - a gas at ordinary temperatures and a colorless, volatile, flammable liquid when compressed; used as a solvent, as a refrigerant, and in the manufacture of tetraethyl lead. Silicon Tetrachloride (C2H5Cl) - a gas at ordinary temperatures and a colorless, volatile, flammable liquid when compressed; used as a solvent, as a refrigerant, and in the manufacture of tetraethyl lead. Trichlorosilane - a chemical compound containing silicon, hydrogen, and chlorine. At high temperatures it decomposes to produce silicon, and therefore purified trichlorosilane is the principal source of ultrapure silicon in the semiconductor industry. In water, it rapidly decomposes to produce a silicone polymer while giving off hydrochloric acid. Because of its reactivity and wide availability it is frequently used in the synthesis of silicon-containing organic compounds. Fluorine (F) - a poisonous, pale, yellow-green gas that is the most chemically reactive of all the elements. It is highly dangerous in its pure form and can cause severe burns if it comes into contact with the skin. Boron Trifluoride (BF3) - a pungent, colorless toxic gas that forms white fumes in moist air. It is a useful Lewis acid and a versatile building block for other boron compounds. Sulfur Hexafluoride (SF6) - one of the most popular insulating gases (next to air). It is nonflammable, non-toxic, moderately inexpensive, and a good insulator because of its electronegativity. SF6 has a breakdown strength of about three times that of air. At normal temperatures it is non-corrosive and fairly inert; however, at temperatures above 500C SF6 decomposes. The decomposition products (i.e., fluorine) react with most substances, especially any water vapor. Tungsten Hexafluoride - an inorganic compound with the formula WF6. This corrosive, colorless compound is the densest known gas at a pressure of 1 atm and room temperature (25 C). The gas is most commonly used in the production of semiconductor circuits and circuit boards through the process of chemical vapor deposition.

Other notable gases:

Arsine (AsH3) - a flammable and toxic gas. Synonyms include arseniuretted hydrogen, arsenous hydride, arsenic trihydride, and hydrogen arsenide. Diborane (B2H6) - a colorless gas with a repulsive, sweet odor. It mixes easily with air and will ignite spontaneously in humid air at room temperatures. Diborane is a respiratory irritant. Symptoms can occur immediately or be delayed for up to 24 hours after exposure. Germane (GeH4) - a flammable, toxic, colorless gas that reacts with oxidizers and halogens. Mercaptans and Sulfur Compounds 20130408 40

Tungsten (VI) fluoride (WF6) - also known as tungsten hexafluoride. This corrosive, colorless compound is the densest known gas at a pressure of 1 atm and room temperature (25 C). The gas is most commonly used in the production of semiconductor circuits and circuit boards through the process of chemical vapor deposition. Phosphine (PH3) -a colorless, spontaneously flammable, poisonous gas that has a fishy odor. It is used as a doping agent for solid-state components. Phosgene (COCl2) - a colorless, volatile liquid or gas known as a poison gas but used widely in making glass, dyes, resins, and plastics. Silane (SiH4) - a colorless gas that is both flammable and pyrophoric (i.e., capable of igniting spontaneously upon contact with air). It has a repulsive odor. Silane is used as a silicon source for the epitaxial deposition of single-crystal and polycrystalline silicon, for the low temperature chemical vapor deposition of silicon dioxide, and for the chemical vapor deposition of silicon nitride films. It also is used for growth of amorphous silicon films.

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Pressurization and Explosion Cryogenic liquids vaporize with a volume change ratio of 700-900 can cause violent changes in pressure, particularly if this occurs in a confined space. This in turn can result in an explosion. Vent systems must be in place to allow gas to escape from confined spaces. Pressurization can occur due to the following: 1. Ice forming on the venting tube, plugging it and preventing gas release. 2. Damaged equipment resulting in cryogenic fluids leaking into small areas, upon vaporization the cryogenic liquid vaporizes and causes pressure build up. 3. Loss of vacuum inside a cryostat or Dewar. 4. If a liquid helium-cooled superconducting magnet "quenches" (changes spontaneously from a superconducting state to a normal state). 5. Liquid nitrogen having permeated through sealed cryotubes containing samples which then return to room temperature. 6. Direct contact of the cryogenic liquid with water in a tube results in rapid vaporization of the cryogenic liquid and can cause the tube to explode. E. Damage to Equipment The very cold temperatures of cryogenic liquids can damage equipment and materials, which can result in danger. Examples of damage include the following: 1. Spilled liquid nitrogen can crack tiles and damage flooring such as vinyl. 2. Rubber tubing may become brittle and crack during use. 3. Condensation of water around electrical cables may result in an electrical shock hazard. F. Flammable gas - Hydrogen Hydrogen is extremely flammable and should be treated with extreme caution. Areas of use should be restricted, clearly marked and well ventilated. No naked flames, electrical ignition sources, sources of static electricity, or potentially combustible materials should be allowed within the restricted area as any of these could result in an explosion if gas has escaped.

Liquid hydrogen can condense and solidify air resulting in an explosion hazard. For this reason closed hydrogen systems should be used to prevent backflow of air.

GENERAL SAFETY PRACTICES

A. Personnel Safety 1. Face shields and goggles shall be worn during the transfer and normal handling of cryogenic fluids. 2. Loose fitting, heavy leather, or other insulating protective gloves shall be worn at all times when handling cryogenic fluids. Shirt sleeves will be rolled down and buttoned over glove cuffs, or an equivalent protection such as a lab coat will be worn in order to prevent liquid from spraying or spilling inside gloves. Pants without cuffs will be worn.
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B. Safety Practices 1. Cryogenic fluids must be handled and stored only in containers and systems specifically designed for these products and in accordance with applicable standards, procedures, or proven safe practices. 2. Transfer operations involving open cryogenic containers, such as dewars, must be conducted slowly to minimize boiling and splashing of the cryogenic fluid. Transfer of cryogenic fluids from open containers must occur below chest level of the person pouring liquid. 3. Such operations shall be conducted only in well ventilated areas to prevent the possible gas or vapor accumulation, which may produce an oxygen-deficient atmosphere and lead to asphyxiation. The volumetric expansion ratio between liquid and atmospheric nitrogen is approximately 700 to 1. 4. Equipment and systems designed for the storage, transfer, and dispensing of cryogenic fluids shall be constructed of materials compatible with the products being handled and the temperatures encountered. There is no single source of information that will provide exact specifications and standards for cryogenic equipment. ASME Codes B31.1 through B31.7 apply, ASME Code B31.3 contains the majority of the relevant information. The American Society of Testing Materials (ASTM) handbook provides information concerning tensile strength of metals at various temperatures and other relevant information. The Code of Federal Regulations, 49 CFR, provides some useful guidelines, although it only references cryogenic vessels used in rail transportation. In each case, the design specifications are left to the discretion of the designing engineer. 5. All cryogenic systems, including piping, must be equipped with pressure-relief devices to prevent excessive pressure build-up. Pressure-reliefs must be directed to a safe location. It should be noted that two closed valves in a line form a closed system. The vacuum insulation jacket should also be protected by an over-pressure device if the service is below 77 Kelvin. In the event a pressure-relief device fails, do not attempt to remove the blockage; instead call EH&S immediately. 6. If liquid nitrogen or helium traps are used to remove condensable gas impurities from a vacuum system that may be closed off by valves, the condensed gases will be released when the trap warms up. Adequate means for relieving the resultant build-up of pressure must be provided.

VII. SPECIFIC PROCEDURES

A. REFILLING DEWARS IN LABORATORIES 1. Never refill Dewars or transfer cryogenic liquids alone! 2. Make sure that there is good ventilation. Open a door if you are in a small room. 3. Remove watches, rings and other metal jewelry on hands and wrists 4. Wear required Personal Protective Equipment identified in the PPE hazard assessment (29 CFR 1910.133). In general the following PPE is the minimum acceptable: a. Cryogenic gloves.

b. Lab coat with sleeves pulled over cuffs of cryogenic gloves.

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c. Full length cuffless pants that extend over shoes tops. d. Closed-toed shoes that are impervious to liquids, such as leather, or covered with liquid proof shoe covers/spats. e. Safety Glasses or Chemical Splash Goggles and a Full Face Shield. 5. Use Dewars rated for the cryogen being transferred. a. Never use a Dewar that does not have a pressure relief valve or pressure venting lid/stopper. b. Use pressure venting lids/stoppers supplied by the Dewar manufacturer. c. Never use Dewars with makeshift or homemade lids/stoppers. d. Glass Dewars must be taped solidly around the outside. The plastic mesh which comes with some small thermos bottles primarily provides some protection for the Dewar, but does not necessarily protect against glass shards resulting from implosion.
6. Dewars larger than 20 Liters will be lifted and poured by two people. 7. Never use a funnel as during overfill cryogenic liquid may be propelled upward. 8. Ensure the receiving vessel is dry.

9. The receiving vessel must be raised so the delivery tube is immediately above the mouth of the vessel (i.e., the cryogenic liquid should never be allowed to fall through air to reach the receiving vessel). Use a table, cart or other mechanical means to position the vessel in the proper location. Never hold the vessel with unprotected hands while filling. 10. To reduce thermal shock, first cool the receiving vessel by dispensing a small amount of cryogenic fluid then continue the dispensing process. Delivery should be conducted slowly to minimize splashing, spilling and thermal shock to the receiving vessel. 11. Do not move or bend the fill tube during filling. 12. Stay out of the vapor pathway during dispensing. 13. Do not leave a filling operation unattended. 14. Only use approved materials with cryogens. Unapproved materials (such as plastic, rubber, wrought iron, hollow tubes, and carbon steel) will become brittle and shatter, or in the case of hollow tubes become over pressurized. 15. Periodically inspect equipment and remove ice and frost blockages from openings to prevent over pressurization. 16. Do not tamper with pressure relief valves. Report any leaks or improperly set relief valves to the manufacturer. 17. Equipment should be kept clean without the use of corrosive cleaning materials that could damage the metal jacket. 18. When manually pouring liquid into a smaller Dewar, assure that the secondary container is secured, pour slowly to prevent excess splashing, do not overfill, and use a phase separator, if available, to control the vapor path while pouring.
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B. TRANSPORT OF CRYOGENIC LIQUIDS Special precautions must be taken to prevent a spill while transporting cryogens in addition to minimizing exposures from liquids and vapors. The high liquid to vapor expansion ratio could rapidly displace all oxygen in a room and result in asphyxiation. Implement the following procedures to minimize exposures: 1. Transport within the laboratory or lab building a. Wear all required PPE (see VII.A.4). b. Use no fewer than two personnel to transport cryogenic liquids and use handcarts equipped with brakes for large Dewars and cylinders. c. Never transport an open container of cryogenic liquid, no matter how small. d. Plan the route of transport. The BEST PRACTICE IS TO AVOID USING AN ELEVATOR. In event of an elevator failure or spill, the space may quickly undergo oxygen displacement. If this is not avoidable, send your buddy to the receiving floor. Then load the Dewar. Remain on the sending floor while you send the Dewar to the receiving floor unmanned. After your buddy unloads the Dewar, join him/her for the rest of the transport. If the transport by elevator takes place over multiple floors, clearly label the Dewar with a warning to anyone who may want to use the elevator between the sending and receiving floors to wait until the transport process is complete. e. Always use care when handling equipment. Damage to Dewars could result in the loss of vacuum and increased evaporation. Transport of helium Dewars requires extra care because they are fragile. f. When at all possible, do not hand-carry cryogenic liquids. For larger Dewars use a stable wheeled base designed for the Dewar transport. Check to ensure stability before commencing transport. g. When carrying a Dewar, make sure it is the only item you are carrying. Hold the Dewar as far away from the face as possible. Be on the lookout for other people who may run into you or bump you. h. Large mobile Dewars used for transport should be equipped with a braking mechanism. Do not use feet to brake. Steel toed boots are recommended. i. Take care to avoid crushing hands or fingers between the vessel or cart and walls or door frames. j. If there is any risk of tipping, a cart should be used. Wheeled trolleys may not be used if the vessel must pass over elevator thresholds or other slots/crevasses wider than 25% of the wheel width. 2. Transport between buildings a. Follow the guidelines above. b. In addition, avoid grates, large cracks in sidewalks/pavements, or other hazards that could cause tripping. c. For transport of large nitrogen Dewars outside -- over pavement, sidewalks, wheelchair curb-cuts a 4-wheel tipcart should be used. The casters welded to the tank, and/or the casters on the trollies in common use, are not meant for transport over pavement and concrete.
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d. While in route exercise great care stay completely clear of sewer grates, large cracks, and/or uneven portions of the pavement, and any other hazards which could catch a cart wheel and cause tipping. 3. Vehicular transport (see note at end of this section) A risk assessment has been conducted. The container of the cryogenic material is labeled with the IUPAC name of its contents and a danger hazard warning sign. The driver has been fully informed as to what is being carried and its associated hazards. The appropriate Personal Protective Equipment has been provided. An information sheet is carried within the vehicle to provide emergency response services with specific data about the material in the event of an accident. The quantity to be transported is consistent with DOT regulations.
NOTE: Transportation of cryogenic substances is covered by the US Department of Transportation (DOT), 49 CFR 173. These regulations cover specific volumes/mass of dangerous goods that may be transported, duties of responsibility, correct packaging and labeling of goods, vehicle usage and driver training. Exceptions for cryogenic liquids can be found in 49 CFR 173.320 as follows: (a) Atmospheric gases and helium, cryogenic liquids, in Dewar flasks, insulated cylinders, insulated portable tanks, insulated cargo tanks, and insulated tank cars, designed and constructed so that the pressure in such packagings will not exceed 25.3 psig under ambient temperature conditions during transportation are not subject to the requirements of this subchapter when transported by motor vehicle or railcar except as specified in paragraphs (a)(1), (a)(2), and (a)(3) of this section. (1) Sections 171.15 and 171.16 of this subchapter pertaining to the reporting of incidents, not including a release that is the result of venting through a pressure control valve, or the neck of the Dewar flask. (2) Subparts A, B, C, and D of part 172, (Secs. 174.24 for rail and 177.817 for highway) and in addition, part 172 in its entirety for oxygen. (3) Subparts A and B of part 173, and Secs. 174.1 and 177.800, 177.804, and 177.823 of this subchapter.

C. STORAGE OF CRYOGENIC LIQUIDS

A cryogenic liquid storage unit left open to the atmosphere, or catastrophic failure of a storage unit, could create an oxygen deficient atmosphere. Follow these procedures to reduce the likelihood of this occurrence:

1. Glass Dewars must have an exterior coating/cover to minimize projectiles in the event of an explosion. Newer Dewars may have a plastic mesh over the exterior for this purpose. Older Dewars must be thoroughly taped or replaced. a. NEVER take liquid nitrogen or other cryogenic fluids in a car or a van where the driver's compartment is not segregated and sealed from the load. The load compartment of the van must be ventilated. Where a specimen needs to be transported frozen, consider whether dry ice would be suitable since it reduces the risks. 46

b. Before transporting cryogens, ensure that the following have been addressed: Only store Dewars in well-ventilated rooms with a minimum of six air changes per hour. 3. If the ventilation rate is unknown, contact EH&S and Facilities Management (FACMAN) to evaluate the storage area. 4. EH&S and/or FACMAN may recommend the installation of oxygen detection systems and alarms for cryogenic liquid storage areas depending on location, ventilation, and quantity of material stored. 5. Do not store cryogenic liquids with corrosive or flammable chemicals. 6. Storage units should be placed so that vents and openings are oriented away from personnel and lab equipment. 7. Bulk cryogenic liquid dispensing areas within buildings must be well ventilated. EH&S recommends continuous oxygen monitoring equipment in all these areas. All new installations should be designed with oxygen monitoring system and alarm. 8. Storage of cryogenic liquid Dewars in hallways, unventilated closets, environmental rooms, and stairwells is prohibited. 9. No more than one backup Dewar is allowed per piece of equipment using cryogenic liquids in research labs. Additional Dewars must be stored in areas designed for such storage. Contact EH&S to evaluate potential storage locations.

D. EMERGENCY PROCEDURES AND FIRST AID

Liquid Nitrogen (LN2) is the most commonly used cryogenic liquid. Oxygen depletion resulting from nitrogen gas may occur rapidly with no warning properties. A person entering an oxygen deficient environment may become disoriented and unable to respond properly. Nitrogen gas is odorless, colorless, tasteless, and inert. The failure of a large Dewar could spill 180 L of LN2 which in gas form will completely displace all oxygen in a 21x21x10 ft room. A much smaller spill in the same room could still create a safety hazard. Simply reducing the oxygen content in a room below 19.5 % is considered an oxygen deficient environment. Implement the following procedures to minimize the risk of asphyxiation: 1. If ventilation in the room is less than six air changes per hour, contact EH&S for advice about installing oxygen level detection alarm. 2. If a spill occurs, immediately exit the area. With adequate ventilation, it may be appropriate to return to the area after thirty minutes. For large spills, contact EH&S immediately as the area may need to be monitored for oxygen levels area and determine when it is safe to re-enter. 3. If experiencing symptoms such as lightheadedness, dizziness, or confusion, immediately seek fresh air and receive medical attention. 4. If an employee becomes unconscious in a cryogenic liquid storage area they should only be retrieved by personnel using proper PPE (such as a Self Contained Breathing Apparatus). ASU does not have the proper equipment to mount an extraction in a confined or oxygen deficient space; therefore the fire department should be immediately notified (911). Over fifty percent of deaths associated with asphyxiation in confined spaces occur to would-be rescuers.

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5. Once personnel have been removed to fresh air, provide rescue breathing or CPR until paramedics arrive. In the event that skin or the eyes come into contact with cryogenic gases or liquid, follow first aid procedures, then immediately seek medical attention. 6. Immediately remove any clothing that has been contaminated. In the event of clothing contamination with oxygen, hydrogen, or carbon monoxide, it is important to remove clothing, evacuate personnel from the facility, and keep away from ignition sources. 7. Flush or soak the area with warm water (no greater than 105oF). 8. Do not apply dry heat or rub damaged flesh or eyes. 9. Employees should notify their supervisor of injuries and complete the ASU EH&S Accident/Near Miss/Quality Improvement Report located at the following web address: http://www.asu.edu/uagc/EHS/incident_employee.htm. If medical evaluation and follow up is required, employees should report to: Tempe St. Lukes Hospital, 1500 South Mill Avenue, Tempe, Arizona, (480) 968-9411.

E. SPILLS AND DISPOSAL 1. MINOR SPILL ( 1 liter) a. Allow liquid to evaporate, ensuring adequate ventilation. b. Following return to room temperature, inspect area where spillage has occurred. c. If there is any damage to the floors, benches or walls, report it to Facilities Management. d. If any equipment has been damaged following the spillage, inform your Mission Manager, OSS and the Safety & Mission Assurance Office. 2. MAJOR RELEASE ( 1 liter) a. Shut off all sources of ignition. b. Evacuate area of all personnel. c. Inform EH&S and supervisor. d. DO NOT return to the area until it has been declared safe by EH&S. 3. DISPOSAL Care needs to be taken when disposing of cryogenic liquids. DO NOT pour cryogenic liquids down the sink they will crack waste pipes causing potentially dangerous leaks store cryogenic substances or allow them to vaporize in enclosed areas, including: fridges, cold rooms, sealed rooms and basements ensure that the area in which the cryogenic liquid is left to vaporize is well ventilated

DO NOT

DO

TRAINING
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Training should be given in all aspects of the use and handling of cryogenic materials. A combination of on the job skills, instructions and information covering the following areas provides a minimum standard to which all users must be trained: 1. Understanding of the Material Safety Data Sheet (MSDS), the risks involved and where to obtain information. 2. Understanding the risks and effects of oxygen depleted atmospheres. 3. Conducting a risk assessment. 4. Use of Personal Protective Equipment (PPE). 5. Handling cryogenic materials. 6. Moving containers of cryogenic materials ( 1 liter). 7. Emergency procedures. 8. Spillage procedures. And if necessary 9. Manual handling of larger storage vessels 10. Dispensing bulk quantities (> 1 liter) 11. Vehicular transportation and delivery of cryogenic materials Much of the training will be carried out as on the job training and should be done by a competent person within the lab group. Individual training records shall be kept for each person handling cryogenic substances by the PI who shall maintain this information within the posted Laboratory Training Records, as required by ASU CHP.

VIII. REFERENCES

- CGA P-12-1993, Safe Handling of Cryogenic Liquids - CGA S-1.1, Pressure Relief Device Standards- Part 1-Cylinders for Compressed Gases [6] - CGA S-1.2, Pressure Relief Device Standards- Part 2-Cargo and Portable Tanks for Compressed Gases [7] - CGA S-1.3, Pressure Relief Device Standards- Part 3-Compressed Gas Storage Containers [8] - CGA V-1, American National, Canadian, and Compressed Gas Association Standard for Compressed Gas Cylinder Valve Outlet and Inlet - ASME Boiler and Pressure Vessels Code Section VIII, Division 1 49

- NFPA 45, Fire Protection for Laboratories Using Chemicals - ACS Handbook of Chemical Health and Safety, Robert J. Alaimo, ed. Oxford University Press, 2001 - CRC Handbook of Laboratory Safety, 2nd edition, Norman V. Steer, ed., CRC Press, 1985. - Numerous college and university EH&S web sites, including, but not limited to Cornell, U Del, Purdue, UMI, UNR, Princeton and U Dundee.

When to Replace a Hose Restraint

Signs of wear, which would indicate a hose restraint needs to be replaced, include: 1. 2. 3. 4. 5. Bird caging of the wires Rust Broken wires or strands Visible bubbles in the unit either slack or when fitted to the hose Heat damage

Key Safety Points

Regularly inspect hose restraints for signs of damage and wear. Replace a damaged hose restraint must be immediately. Immediately following a failed hose event, inspect hose restraints used for damage thoroughly. Ensure the hose restraint is stamped with its size range, strength and serial number for traceability Ensure the hose restraint is fitted in accordance with strict fitting procedures. Ensure hose restraints are stored in a clean dry environment. Never use a hose restraint on a hose of incorrect size. Never push the mouth of the hose restraint against a flat surface

Experimenters use of vacuum pumping on the pad

If the pump is a steady state and no switching will occur during preliminary arming then it could remain on, but if voltage/current are detected during mating with a pump on transport cart (Example: Cirtain missions, and few others had pumps on while transporting them to the rail) then the pump will have to be shut off. Normally takes LV crew members an hour or more for mating and arming of the ORSA and/or Belly Band. After the Boom test (initial turn-on test), preliminary arming of the ORSA or Belly Band if the pump is a steady state pump could remain on, but if voltage/current is detected then the pump will have to be turned off before resuming arming.

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1. Pump prior to arming and during FTS checks on the pad (prior to converting systems to Cat A). 2. Prior to arming, switch vacuum pumps off (pad does not have to be cleared since we are still Cat B). 3. After arming, clear pad and switch pumps back on, remotely. 4. While pumping, the pad can be opened as long as we follow all the POWER ON rules (onoff three times, stay on for 5 min, get OSS approval, work external to the vehicle). 5. Clear the pad for ALL switching operations after pad arming (while any system is Cat A).

OSS CHECKLIST PROJECT________________ Operation- Cryogenics

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Date:

______________

OPERATIONS SAFETY SUPERVISOR: ___________________________ PROCEDURE USED: ________________________ CHECK BOX

OPERATION

Verify that procedure is approved Verify all equipment used has been calibrated and certified Verify that oxygen sensors are in place and operable (See Note 1) Verify that area being used has adequate ventilation Verify that only active and essential personnel are in the designated danger area Verify all essential personnel are wearing proper PPE Verify high pressure flex hoses have been calibrated and certified Verify all high pressure flex hoses have been restrained Verify hazard controls such as warning lights, roadblocks and warning signs are in place. Has GSFC Form 23-81, Hazards Analysis Checklist been completed by the experimenter team and reviewed by the OSS Reviewed MSDS for cryogenic(s) used for the operations Brief contingency plan in event of emergency Perform Haz-Op briefing
Note 1

Degrees of asphyxia will occur when the oxygen content of the working environment is less than 20.9% by volume. Effects from oxygen deficiency become noticeable at levels below ~18% and sudden death may occur at ~6% oxygen content by volume. This decrease in oxygen content can be caused by a failure/leak of the cryogenic vessel or transfer line and subsequent vaporization of the cryogen.
803-OSSCL-CR-

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