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Safety in the

Handling of
Cryogenic Fluids
THE INTERNATIONAL CRYOGENICS MONOGRAPH SERIES

General Editors K. D. Timmerhaus, Chemical Engineering Department


University of Colorado. Boulder. Colorado
Alan F. Clark, National Institute of Standards and Technology
Electricity Division. Gaithersburg. Maryland
Carlo Rizzuto, Department of Physics
University of Genoa. Genoa, Italy
Founding Editor K. Mendelssohn, F.R.S. (deceased)

Current volumes in this series

APPLIED SUPERCONDUCTIVITY,
METALLURGY, AND PHYSICS OF
TITANIUM ALLOYS. E. W. Collings
Volume 1: Fundamentals
Volume 2: Applications
CRYOCOOLERS. G. Walker
Part 1: Fundamentals
Part 2: Applications
CRYOGENIC PROCESS ENGINEERING
Klaus D. Timmerhaus and Thomas M. Flynn
HEAT TRANSFER AT LOW
TEMPERATURE. W. Frost
HELIUM CRYOGENICS
Steven W. Van Sciver
MODERN GAS-BASED TEMPERATURE
AND PRESSURE MEASUREMENTS
Franco Pavese and Gianfranco Molinar
POL YMER PROPERTIES AT ROOM AND
CRYOGENIC TEMPERATURES. Gunther Hartwig
SAFETY IN THE HANDLING OF CRYOGENIC
FLUIDS. Frederick J. Edeskuty and Walter F. Stewart
ST ABILIZA TION OF SUPERCONDUCTING
MAGNETIC SYSTEMS. V. A. AI'tov,
V. B. Zenkevich, M. G. Kremlev, and V. V. Sychev
SUPERCONDUCTING ELECTRON-OPTIC
DEVICES. 1. Dietrich
SUPERCONDUCTING MATERIALS
E. M, Savitskii, V. V. Baron, Yu. V. Efimov,
M. 1. Bychkova, and L. F. Myzenkova
Safety in the
Handling of
Cryogenic Fluids

Frederick J. Edeskuty
and
Walter F. Stewart
Los Alamos National Laboratory (Retired)
Los Alamos, New Mexico

Springer Science+ Business Media, LLC


Library of Congress Cataloging-1n-Pub1Ication Data

Edeskuty, F. J .
S a f e t y in t h e h a n d l i n g of cryogenic f l u i d s / F r e d e r i c k J .
Edeskuty, Walter F. S t e w a r t .
p. cm. (The i n t e r n a t i o n a l c r y o g e n i c s monograph s e r i e s )
Includes bibliographical references (p. - ) and index.
ISBN 978-1-4899-0309-9
1. Low t e m p e r a t u r e e n g i n e e r i n g S a f e t y measures. I. Stewart,
Walter F. I I . T i t l e . I I I . S e r i e s .
TP481.E34 1996
621.5'9*0289dc20 96-15817
CIP

ISBN 978-1-4899-0309-9 ISBN 978-1-4899-0307-5 (eBook)


DOI 10.1007/978-1-4899-0307-5

1996 Springer Science+Business Media New York


Originally published by Plenum Press, New York in 1996
Softcover reprint of the hardcover 1st edition 1996

10987654321

All rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form
or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise,
without written permission from the Publisher
To E. F. Hammel, Jr.

Along with his numerous contributions to almost every facet


of cryogenics, too many to mention here, he has also been
responsible for the encouragement and training of many
others who have contributed greatly to the knowledge and
application of cryogenics. Dr. Hammel introduced cryogenics
to the Los Alamos National Laboratory and was responsible
for founding and leading a cryogenics group that attained
worldwide recognition for its excellence. He has served as a
mentor and an inspiration to the authors and to many others
who have gone on to gain their own recognition.
Preface

The importance of safety in any scientific endeavor is never in question. However,


when cryogenic temperatures are involved, safety is especially important. In
addition to observing the normal precautions, one must also take into account the
variations of physical properties that occur at low temperatures. At these tempera-
tures, some properties not only exhibit large differences from their normal values
but also can vary widely over a small temperature range. Before any cryogenic
project is started, a thorough knowledge of the possible hazards is necessary. Only
in this way can the safest operation be attained. Over the hundred-year history of
cryogenic research, this has been shown to be the case. Keeping this requirement
in mind is an essential ingredient in the quest for accident-free work.
The past four or five decades have seen a great expansion of cryogenic
technology. Cryogenic liquids, such as oxygen, nitrogen, hydrogen, and helium,
have become commonly used in a number of different applications and are easily
available in any part of the United States and, indeed, almost anywhere in the world.
Not only are these liquids available, they have become less expensive and also
available in ever larger quantities. As quantities increase, so also do the conse-
quences of mishaps. The future seems to hold promise of ever larger and more
widespread use of the common cryogens. Thus, the importance of safety also
increases as time progresses.
This book is not the first to address the subject of safety in the handling of
cryogenic fluids, nor will it be the last. Since its publication by Plenum Press about
25 years ago, Safety with Cryogenic Fluids by M. G. Zabetakis has been the most
authentic treatise on the subject of cryogenic safety. Details of many cryogenic
hazards are skillfully discussed in this book. Even today, this book should be
required reading for the newcomer to cryogenic technology. Despite its age, the
information contained therein is invaluable. In this situation it might be asked, why
another book on safety in handling cryogenic fluids? As cryogenic systems become
more common and the quantities of cryogenic fluids become larger, the importance
of safety is taken more and more seriously and regulations become stricter. Because
vii
viii Preface

of the ever increasing costs of errors that lead to accidents, such errors can cause
the termination of what might have been a beneficial program.
The striving for safety in any field must be a continuing effort as long as new
production methods and new applications are developed. Since the writing of Safety
with Cryogenic Fluids, a great deal of research and development in cryogenic
technology has resulted in additional safety-related data and knowledge. Some of
this work has occurred because of accidents, and more of it has been done in time
to prevent accidents.
It is not our intention to replace or supplant the previous book. Rather, we
would like to add the benefit of our combined cryogenic engineering experience,
which now totals over 75 years, most of which has taken place since the writing of
Safety with Cryogenic Fluids. One of the later chapters in our book is devoted to
pointing out the necessity for continued research related to safety in the use of
cryogens. Hopefully, this book can take its place alongside Zabetakis's work when
the occasion arises that a subsequent book will further elucidate the issues to be
addressed in continuing safety research.
Because the present work is based on the experience of the authors, the subjects
contained herein are somewhat limited to our areas of experience. Other safety topics
are covered adequately in the Zabetakis book. Also, there is a constantly increasing safety
literature appearing in such publications as the proceedings of the biannual Cryogenic
Engineering Conference and International Cryogenic Engineering Conference. Safety is
always an important part of these conferences and other cryogenic symposia.
After an introductory chapter, Chapter 2 discusses the physiological hazards
accompanying the use of cryogens. Chapter 3 covers the phenomenon of embrit-
tlement of structural materials, and Chapter 4 contains a discussion of the stresses
that can occur because of the large temperature excursions, both static and transient,
that accompany work in the realm of cryogenics. Chapter 5 considers the potential
for pressure, buildup in a system containing a cryogen, and Chapter 6 covers the
potential hazard of condensation of higher boiling substances when subjected to
the colder temperatures of the cryogens. Chapters 7 and 8 deal with the hazards of
combustion of the combustible cryogens, namely, methane and hydrogen, and their
relevant properties. The great potential for increased use of these two substances
as cryogens makes this a topic that will assume ever greater importance, and
consequently a field for rapidly expanding work on their safety.
Chapter 9 gives a discussion of safety problems that arise in the handling of
liquid oxygen, and Chapter lOis devoted to the discussion of slush hydrogen, an
esoteric fluid that might find large-scale use in aerospace applications. Chapter 11
considers the existing guidelines, standards, rules, and regulations for the handling
of cryogenic fluids, and Chapter 12 outlines areas where future safety research work
is warranted. Chapter 13 presents a discussion of accidents about which the authors
have some knowledge, fortunately from the standpoint of being investigators rather
than perpetrators.
Preface ix

This book is written mainly in SI units, with the more common United States
Customary System units frequently included in parentheses for the convenience of
the reader.
Frederick J. Edeskuty
Walter F. Stewart
Los Alamos, New Mexico
Acknowledgments

The authors wish to acknowledge the patience and understanding of their wives,
Jeanette Bergren Edeskuty and Marleen Stewart. Without their constant encourage-
ment and understanding, the completion ofthis book would not have been possible.
We also wish to thank emergency room physician Dr. Celeste E. Puckett for
reviewing Chapter 2 and offering many helpful comments to improve its content.

xi
Contents

Chapter 1 Introduction ...................................... .


1.1. General Safety Requirements. . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Cryogenic Fluids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3. Types of Hazards. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

Chapter 2 Physiological Hazards. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9


2.1. Cold Damage to Living Tissue. . . . . . . . . . . . . . . . . . . . . . 9
2.1.1. Freezing of Tissue. .. . .. .. . .. . . . .. .. . .. . . .. . . 9
2.1.2. Hypothermia. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 10
2.1.3. Prevention of Cold Damage to Tissue. . . . . . . . . .. 10
2.1.4. Treatment of Cold Damage. . . . . . . . . . . . . . . . . . .. 11
2.2. Asphyxiation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12
2.3. Toxicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 16

Chapter 3 Embrittlement of Materials . . . . . . . . . . . . . . . . . . . . . . . . .. 19


3.1. Low-Temperature Embrittlement. . . . . . . . . . . . . . . . . . .. 19
3.2. Hydrogen Embrittlement . . . . . . . . . . . . . . . . . . . . . . . . .. 24
3.2.1. Hydrogen Reaction Embrittlement. . . . . . . . . . . . .. 24
3.2.2. Internal Hydrogen Embrittlement. . . . . . . . . . . . . .. 25
3.2.3. Environmental Hydrogen Embrittlement. . . . . . . .. 26
3.2.4. Hydrogen Embrittlement Mechanisms. . . . . . . . . .. 28
3.2.5. Avoiding Hydrogen Embrittlement ....... . . . . . .. 29
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 31

xiii
xiv Contents

Chapter 4 Stresses Caused by Thermal Contraction. . . . . . . . . . . . . .. 33


4.1. Stresses Caused by Dimensional Change
(Steady-State Temperature) . . . . . . . . . . . . . . . . . . . . . . .. 33
4.1.1. Storage and Transport Vessels . . . . . . . . . . . . . . . .. 36
4.1.2. Transfer Lines and Piping Systems . . . . . . . . . . . .. 41
4.2. Stresses Caused by Thennal Gradients ............... 43
4.3. Other Stress Considerations. . . . . . . . . . . . . . . . . . . . . . .. 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 51

Chapter 5 Buildup of Pressure in Closed Systems. . . . . . . . . . . . . . . .. 53


5.1. Considerations in Calculating the Rate of Pressure Rise
in a Closed System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 55
5.2. Overpressure Protection .......................... 63
5.3. Thennal Expansion as a Source of Overpressure. . . . . . .. 65
5.4. Pressure Oscillations as a Source of Overpressure ...... 66
5.4.1. Flow Oscillations . . . . . . . . . . . . . . . . . . . . . . . . . .. 66
5.4.2. Thennal Acoustic Oscillations. . . . . . . . . . . . . . . .. 68
5.5. Rollover . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 69
5.6. Quenching of Superconducting Magnets. . . . . . . . . . . . .. 70
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 71

Chapter 6 Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 73
6.1. Hazards Arising from Unwanted Condensation. . . . . . . .. 74
6.1.1. Condensation and Freezing ofInert Substances. . .. 74
6.1.2. Condensation of Substances F onning Combustible
Mixtures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 75
6.1.3. External Condensation on Cold Surfaces. . . . . . . .. 76
6.2. Preventive Measures. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 77
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 77

Chapter 7 Combustion Hazards. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79


7.1. Fire Prevention. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79
7.1.1. Ignition Sources . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79
7.1.2. Elimination of Combustible Mixtures . . . . . . . . . .. 81
7.2. Release of Combustible Gas to the Atmosphere. . . . . . .. 86
7.2.1. Unflared Venting. . . . . . . . . . . . . . . . . . . . . . . . . . .. 86
7.2.2. Flared Venting. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 87
Contents xv

7.2.3. Venting versus Flaring. . . . . . . . . . . . . . . . . . . . . .. 90


7.3. Fire Protection and Response. . . . . . . . . . . . . . . . . . . . . .. 93
7 A. Combustion Accident Causes and Consequences . . . . . .. 94
704.1. Blast Overpressure. . . . . . . . . . . . . . . . . . . . . . . . .. 95
704.2. Thermal Radiation. . . . . . . . . . . . . . . . . . . . . . . . .. 95
704.3. Protection from Combustion Accidents. . . . . . . . .. 98
References ......................................... 100

ChapterS Combustion Properties .............................. 101


8.1. Deflagration .................................... 101
8.2. Detonation ...................................... 110
8.3. Detonation Studies ............................... 111
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

Chapter 9 Oxygen Hazards. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117


9.1. Properties of Oxygen and Consequent Hazards. . . . . . . . . 117
9.2. Ignitability Tests ................................. 120
9.3. Materials for Liquid-Oxygen Service ................. 123
9.3.1. Metals .................................... 123
9.3.2. Nonmetals ................................. 125
904. Cleaning for Oxygen Service ....................... 128
9.5. Operational Precautions ........................... 130
9.6. Air Condensation ................................ 130
9.7. Ozone ......................................... 131
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

Chapter 10 Slush Hydrogen . ................................... 133


10.1. Advantages of Slush Hydrogen .................... 133
10.2. Properties of Slush Hydrogen ...................... 135
10.2.1. Equation-of-State Relationships .............. 135
10.2.2. Vapor Pressure ........................... 137
10.2.3. Melting Curve ............................ 138
10.204. Heat of Transition ......................... 139
10.2.5. Electrical Conductivity ..................... 141
10.2.6. Equilibrium between Orthohydrogen and
Parahydrogen ............................ 141
10.2.7. Solubility of Helium in Liquid or Slush
Hydrogen ............................... 142
xvi Contents

10.3. Potential Safety Hazards of Slush Hydrogen ......... 144


10.3.1. System Pressure Variability ................. 144
10.3.2. Pressure Oscillations ....................... 145
10.3.3. Volume Expansion upon Melting and Warming .. 146
10.3.4. Electric Charge Buildup in Flowing Slush
Hydrogen ............................... 146
10.3.5. Aging Effects in Large Storage Quantities ...... 146
10.3.6. Conversion of Orthohydrogen to Parahydrogen 146
10.3.7. Helium Effectiveness in Pressure Control ...... 147
10.4. Preventive Measures ............................. 147
10.4.1. System Design ........................... 147
10.4.2. Production Techniques ..................... 149
10.4.3. Materials Selection ........................ 150
10.4.4. Storage, Aging, and Upgrading .............. 150
10.4.5. Pressure Control .......................... 151
10.4.6. Fluid Quantity Measurements ............... 152
10.4.7. Thermal Acoustic Oscillations ............... 153
10.4.8. Volume Expansion ........................ 153
10.4.9. Operational Criteria ....................... 153
10.5. Conclusion .................................... 156
References ......................................... 156

Chapter 11 Guidelines, Standards, and Regulations ................ 159


11.1. Guidelines and Standards ......................... 160
11.2. Codes and Regulations ........................... 175
11.3. Hydrogen Standards and Regulations ............... 177
11.4. Conclusion .................................... 178
References ......................................... 178

Chapter 12 Safety Problems Needing Further Investigation ......... 181


12.1. Dispersion of Leaks and Spills ..................... 181
12.1.1. Liquid-Cryogen Spills or Vapor Releases
without Combustion ....................... 182
12.1.2. Liquid-Cryogen Spills or Vapor Releases
with Possible Combustion .................. 183
12.2. Spills of Liquid Cryogens onto Water Surfaces ........ 183
12.3. Hydrogen Combustion ........................... 184
12.3.1. Ignition of Hydrogen Releases ............... 184
12.3.2. Venting versus Flaring ..................... 185
Contents xvii

12.3.3. Transition of Deflagration to Detonation ....... 185


12.3.4. Thermal Effects of Hydrogen Combustion ..... 185
12.3.5. Overpressure Effects of Hydrogen Combustion .. 186
12.4. Slush-Hydrogen Safety Problems .................. 186
12.4.1. Detection of Air Contamination in Liquid and
Slush Hydrogen .......................... 187
12.4.2. Ignition of Solid-Air-Hydrogen Mixtures ...... 188
12.4.3. Confined Combustion ofa Slush-Hydrogen
and Air Mixture ........................... 188
12.4.4. Response to Detection of Air Contamination
in Liquid or Slush Hydrogen ................ 189
12.4.5. Pressure Control .......................... 190
12.4.6. Electric Charge Buildup .................... 191
12.4.7. Long-Term and/or Large-Depth Storage ....... 191
12.5. Quantity-Distance Relationship for Hydrogen Storage .. 192
12.6. Guidelines, Standards, and Regulations .............. 193
References ......................................... 194

Chapter 13 Accidents: Prevention and Examples .................. 197


13.1. Accident Prevention by Design .................... 197
13.2. Accidents in Cryogenic Systems ................... 198
13.2.1. Accidents with Hydrogen ................... 199
13.2.2. Accidents with Liquid Nitrogen .............. 203
13.2.3. Accident with Liquid Helium ................ 208
13.2.4. Accident with Liquid Oxygen ............... 208
13.3. Conclusion .................................... 212
References . ........................................ 212

Appendix A Some Pertinent Details of the Code of Federal Regulations . . 213


Appendix B List of Symbols . .................................... 225
Appendix C List of Acronyms ................................... 229
Index . ........................................................ 231
Chapter 1

Introduction

Although there might be more than one safe way to design, build, and operate a
cryogenic system, the safety of any system depends not only upon the system itself,
but also upon its interaction with other systems. Therefore, a knowledge of accepted
safety practices and experience with existing systems is invaluable to safe operation
either in new or existing cryogenic systems.
In the case of cryogenic systems, safe operation is important for several
reasons. First, and by far the most important, is the necessity of avoiding injury
either to operating personnel or to the general public. This one reason must take
precedence over all other considerations.
Although of lesser importance, the financial losses that can accompany any
accident cannot be ignored. As a rule, cryogenic systems are expensive. For storage
vessels and transfer lines, it is almost always necessary to provide an insulation
system that usually means an additional enclosure (vacuum jacket). This amounts
to paying for two vessels where, with systems operating at ambient temperature,
only one would be required. Also adding to the expense is the sophisticated
technology involved in the interconnections and support systems that are needed
between the fluid container and the vacuum jacket as well as the additional
instrumentation that is frequently required. These factors combine to make cryo-
genic systems more costly.
A third reason for the emphasis on safety, which is ever increasing in impor-
tance, is the negative impact ofthe reaction, or possible overreaction, of the general
public to accidents. The public perception of the safety problems of working with
hydrogen has been referred to as the "Hindenburg syndrome" and has hindered the
development of systems that could safely use hydrogen as an ideal fuel. Another
example is the continuing public apprehension of liquefied natural gas (LNG),
which, at least in part, stems from the LNG storage vessel failure in Cleveland in
1944, in spite of the fact that the cause of that accident is well understood and such
accidents can now be prevented. That the power of public opinion is respected (or
even feared) can be seen in the medical application of nuclear magnetic resonance.
Because of the inordinate fear of the general public of anything containing the word
2 Chapter 1

"nuclear," the euphemism MRI (magnetic resonance imaging) is universally in use,


and one never hears the word "nuclear." Public fear of a project can only cause
problems in the continuation of the work, irrespective of whether it is funded by
the government or by industry, and in many cases can even result in the termination
of the project, even if the public would have benefited from it in the long run.

1.1. GENERAL SAFETY REQUIREMENTS

In order to have a safe cryogenic process, the first requirement is to have a safe
system. This means that safety must be considered in every phase of the system
design, in its fabrication, in the system checkout, and throughout its operation.
Furthermore, it is not enough merely to have a safe system. It is also necessary that
the system be operated in a safe manner. In the past, accidents have been caused by
the extraordinary ingenuity exercised by operators in circumventing, frequently
with good intentions, the safety precautions that were built into a system.
In the design of a new system, safety must be considered from the first
conceptual design all the way through the design process until the final construction
drawings are made. Equipment selection must be made with knowledge of the
conditions to which the materials will be subjected, and appropriate choices of
materials must be made. The system as designed must be able to perform every step
of the intended operation in a safe manner as well as to be able to be stopped at any
point of the operation and come safely to rest. There must be sufficient instrumen-
tation to allow the operators to understand what is happening within the system. In
some cases there must be redundant or duplicate instruments to ensure the avail-
ability of the information needed to carry out safe operation Qr, if necessary, to shut
the system down safely.
At every step, safety advice must be available from safety experts. In all but
the smallest projects, design reviews are necessary, with the review committee
consisting of safety experts and cryogenic engineers as well as knowledgeable
people, who are not directly involved in the project. Initiation of construction must
await the full approval of the review team before proceeding. Safety must be
monitored during the construction phase to see that the fabricated system meets the
safety objectives that were established during the design or that resulted from the
design reviews. Design reviews are an important part of making sure that no safety
precautions have been overlooked. These reviews must have the objective of
determining and pointing out what untoward events might possibly happen that
could lead to injury or fatality or to loss of equipment. A safety analysis is frequently
required by the review committee. This should address the design features that have
been incorporated either to obviate any conceivable accident or at least to mitigate
its consequences. Accidents that must be considered include such possibilities as
pipe or vessel ruptures, inadvertent isolation of systems containing cryogenic
Introduction 3

fluids, portions of the system being struck by uncontrolled vehicles or other objects,
loss of insulating vacuum or other types of insulation failure, and acts of nature
such as earthquakes and floods.
During the system checkout, responsible parties must look for unexpected
behavior or lack of proper operation of any subsystem and be able to explain and
eliminate, if necessary, any such behavior. Leak checking is an important part of
system checkout. Although bubble detection with various leak-detection fluids
might be satisfactory for some situations, in critical areas, such as a possible leak
into a vacuum insulation space, more exacting procedures, such as the use of a mass
spectrometer helium leak detector, will be necessary.
The same kind of attention to safety must continue through the operation of
the facility. Plant maintenance must be carried out with high-quality workmanship,
according to preapproved plans. Plant documentation and operating checklists must
be kept up to date. Frequently this will require the continuing oversight of a safety
committee, also consisting of safety experts, operating personnel, and knowledge-
able persons who are not directly involved with the work. The system must be
designed and operated in accordance with written standard operating procedures
(SOPs) which must address the specific operation and must be kept up to date. All
but the simplest operations must be carried out according to written checklists, and
the available checklists and procedures must be written not only for the expected
operations, but also contingency checklists must be written for every conceivable
deviation from expected operation. If at all possible, the situation of trying to react
to an emergency with on-the-spot decisions is to be avoided. When there is
computer control, automatic response can be incorporated into the system operation
software when feasible. Often, remote operation is advisable. In any case, personnel
access should be restricted to those actually needed in performing the operations.
Even ifall the above is done, the safe operation of the facility still requires the
additional safety factor of well-trained and knowledgeable operators. The operators
must be completely familiar with every phase of operation of all equipment within
the facility. In addition, safety training is also advisable for personnel who would
be responding to emergency situations such as fires or massive leakage from a
cryogenic system.
Pilatre de Rozier must have been very familiar with the combustibility of
hydrogen, considering his experience gained in his lecture demonstrations. On
several occasions, he had succeeded, without injury, in inhaling hydrogen and then
lighting the exhaled hydrogen at the end of a glass tube held in his mouth. When
he tried the more daring experiment of inhaling a mixture of hydrogen and air, the
ensuing explosion left him wondering if he had blown out his teeth.l Later he
decided to fly a balloon across the English Channel. When he decided to place a
hydrogen balloon on top of a Montgolfier balloon, it was pointed out that the
container of highly combustible hydrogen was just above the Montgolfier balloon
with its open flame, needed to heat the contained air. His experience told him that
4 Chapter 1

because of hydrogen's density being about 14 times less than that of air, if the
hydrogen were to leak, it would go up, away from the flame. He neglected to
consider the much stronger effect of convection currents in the atmosphere.
Consequently, as the balloon approached the French coast, a flash of flame was
observed, and Pilatre de Rozier fell to his death.2 This is an example of the fact that
one needs complete knowledge of all of the possible effects in a given system.
Training for the operator must begin with the general fundamentals of the
safety problems to be expected from cryogenic fluids. This should then be followed
by training that more specifically addresses the systems and processes to be
encountered in his or her work. Additional on-the-job training is desirable. How-
ever, training must not consist merely of one operator training the next, who, in
tum, passes the training to a third operator, and so on. By the time that several
successive operators have been trained, some important features of the safety
training will probably have been omitted, and accidents will become more and more
likely. In many cases it is a good idea to provide training for emergency personnel,
fire department personnel, and police, so that if any of these organizations is called
upon to answer an emergency, they can do so in the safest possible way, for the
safety of both the general public as well as themselves.
All SOPs, checklists, and safety rules must be in accordance with existing,
applicable safety codes and government regulations (see Chapter 11). Periodic
checks and safety inspections must be made to ascertain that there is strict adherence
to safety rules and procedures. Checklists and system drawings must be kept up to
date, and safety rules that are no longer applicable must be eliminated or updated
as necessary. Retaining rules that are not applicable tends to weaken the observance
of the necessary rules.
Finally, extra care must be taken in the modification of existing systems. A
modification to an existing system requires careful examination of its conse-
quences. What looks like a simple change can lead to accidents, and this has often
happened.

1.2. CRYOGENIC FLUIDS

There is no universally accepted upper temperature limit to what is considered


a cryogenic fluid. Typically, the normal boiling point (NBP) temperature (at 1 atm
pressure) of the fluid is used in defining a limit. Scott3 used an upper temperature
limit of 123 K, and Be1l4 has suggested 200 K. Zabetakis,5 on the other hand,
proposed that fluids that have a critical temperature below room temperature be
considered as cryogens. Although there are many fluids that could be considered
as cryogens by one criterion or another, the number of fluids that are commonly
Introduction 5

Table 1.1. Some Physical Properties of Cryogens and Other Fluidsa,b

Fluid MW TNBP PI pz P3 Tc Pc !!Jlv VZ/VI Vi VI VI


Helium 4,003 4.2 124.9 16.9 0.178 5.2 0.229 20.3 7.4 701 117
p-Hydrogen 2.016 20.3 70.8 1.34 0.0899 33.0 1.29 446 52.8 788 8.9
a-Deuterium 4.028 23.6 161 2.30 0.179c 38.3 1.65 305 70.0 899 5.6
Tritium 6.032 25.0 257 3.14 0.269c 40.4 1.85 231 81.8 955 4.6
Neon 20.18 27.1 1207 9.58 0.900 44.5 2.73 85.8 126 1341 2.6
Nitrogen 28.01 77.3 808 4.62 1.25 126.2 3.39 199 175 646 1.4
Aird 28.96 78.8 874 1.29 132.6 3.77 205 678 1.2
CO 28.01 81.6 790 4.50 1.25c 132.9 3.50 216 176 632 1.3
Fluorine 37.99 85.0 1502 5.63 1.70 144.3 5.22 175 267 883 0.82
Argon 39.95 87.3 1395 5.77 1.79 150.9 4.90 163 242 779 0.94
Oxygen 32.00 90.2 1140 4.47 1.43 154.6 5.04 213 255 797 0.86
Methane 16.04 111.6 423 1.82 0.717 190.5 4.60 510 232 590 0.87
Ethane 30.07 184.6 544 2.05 1.36 305.3 4.87 490 265 400 0.43
Propane 44.10 231.1 581 2.42 2.01 369.8 4.25 428 240 289 0.28
Ethylene 28.05 169.3 570 2.08 282.9 5.16 481 274 0.48
Krypton 83.80 119.7 2413 8.33 3.75 209.4 5.50 108 289 643 0.69
Ozone 48.00 161.3 1460 261.1 5.53 233 0.41
Xenon 131.3 160.5 3057 5.90 289.7 5.84 95.6 518 0.48
COz 44.01 194.6e 1510 1.98 304.2 7.28 573 762 0.12
R-14 88.oI 145.2 1620 7.62 227.5 3.75 138 212 0.69
R-22 86.46 232.4 1409 4.72 369 4.99 234 299 0.21

a Refs. 5-11.
b Notation: MW, molecular weight; T, temperature (K); p, density (kglm\ P, pressure (MPa); l!Jiv, heat ofvaporization
(kJ/kg); V, volume; VI, vaporization index (Ko cm3/J), based on an ambient temperature of3oo K (see Section 1.2).
Subscripts: NBP, normal boiling point (at 1 atm pressure); 1, liquid at NBP; 2, gas at NBP; 3, gas at 101.325 kPa
(1 atm) and 0 DC; c, at the critical point.
C Estimated as an ideal gas.

d Air is not a single-component substance. The values given are based upon liquid air (21 % 02) and the vapor in
equilibrium with it.
e C02 is a solid at the I-atm sublimation point; heat of sublimination is at 1 atm pressure.

encountered is smaller. Table 1.1 lists some of the physical properties that are of
concern to safety in the use of the more commonly encountered cryogens as well
as a few higher boiling fluids (refrigerants) that are included for comparison. The
ratios of the density of the liquid at its normal boiling point to the density of the
corresponding gas in equilibrium with that liquid and to the density of the same gas
at 0 C and standard atmospheric pressure indicate the expansion that can be
expected as the cryogens first evaporate and then warm up to approach ambient
temperature. The vaporization index, VI, for a given fluid is the ratio of the
6 Chapter 1

temperature difference between an average ambient temperature (300 K) and the


normal boiling temperature to the heat of vaporization per unit volume. Thus, the
VI indicates the relative ease of vaporization and, consequently, the rate at which
the fluid can spread and dilute the oxygen content of the surrounding atmosphere
or the rate at which it can build up pressure if it is confined while it is experiencing
a heat input.
Table 1.1 shows that as the NBP decreases, the VI increases. This is an
indication of the increasing difficulty of working with cryogens as their tempera-
tures decrease. The temperature difference between the cryogen and its ambient
surroundings is the driving force for heat to enter the cryogen storage volume. As
this driving force increases, the volume ofliquid that a given quantity of heat can
evaporate also increases, and this behavior is demonstrated by the behavior of the
VI.
In working with cryogens, it is important to remember that many of the
cryogen's physical properties can be considerably different from the same proper-
ties of the gases at ambient temperature. First, the properties are frequently strong
functions ofthe temperature and will have varied considerably from room-tempera-
ture values. Also, operation with cryogens is frequently performed in the vicinity
of the critical-point temperature or under conditions crossing this temperature. In
the vicinity of the critical point, there are rapid variations in many physical
properties, even to the extent that computer calculations of these properties are less
reliable in this region.

1.3. TYPES OF HAZARDS

The low temperature and relatively high density of cryogens can cause safety
concerns. Hazards in the handling of these fluids can arise in several ways. The low
temperature can freeze living tissue, a phenomenon that has been referred to as
cryogenic "bums" or frostbite. Cryogenic temperatures can also affect structural
materials by causing embrittlement and can also induce unwanted stresses either
as a result of the unavoidable thermal contraction or even as a result of thermal
gradients within a structure. The cryogens have the ability to condense and solidify
substances, such as water vapor or carbon dioxide, that freeze at a higher tempera-
ture, and this can cause safety problems if the resulting solids can block safety relief
passages, or if they can cause erosion in places like valve seats. The great expansion
that can take place when a cryogen evaporates can cause substantial displacement
or dilution of the oxygen content of the local atmosphere. If the expansion is not
allowed, enormous pressures can build up. In the case of some cryogens, their
capability to participate in chemical reactions, such as combustion, or their toxic
nature can result in additional hazards. These hazards can be categorized as
physiological, physical, or chemical.
Introduction 7

REFERENCES
1. Friend, J. N. (1951). Man and the Chemical Elements, Charles Griffin & Company Ltd., London.
2. Sweaton, W. A. (1955). Jean-Fran~ois Pilatre de Rozier, the first astronaut, Ann. Sci. 11(4),349.
3. Scott, R. B. (1988). Cryogenic Engineering, Met-Chern Research Inc., Boulder, Colorado.
4. Bell, J. H., Jr. (1963). Cryogenic Engineering, Prentice-Hall, Englewood Cliffs, New Jersey.
5. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
6. Mills, R. L., and Edeskuty, F. J. (1983). Cryogens and their properties, in Liquid Cryogens (K. D.
Williamson, Jr. and F. J. Edeskuty, eds.), Vol. II, Chap. I, pp. 1-14, CRC Press, Boca Raton, Florida.
7. Jenkins, A. C. (1961). Summary of physical properties, inA~on, Helium, and the Rare Gases (G.
A. Cook, ed.), Chapter X, Interscience Publishers, New York.
8. Gosman, A. L., McCarty, R. D., and Hust, J. G. (1969). Thermodynamic Properties of Argon from
the Triple Point to 300 K at Pressures to 1000 Atmospheres, NSRDS-NBS 27, U.S. Department
of Commerce, National Bureau of Standards, Boulder, Colorado.
9. Prydz, R., and Straty, G. C. (1973). The Thermodynamic Properties of Compressed Gaseous and
Liquid Fluorine, NBS Technical Note 392 (Revised), U.S. Department of Commerce, National
Bureau of Standards, Boulder, Colorado.
10. Liley, P. E. (1987). Thermodynamic properties of substances, in Mark's Standard Handbook/or
Mechanical Engineers (E. A. Avallone and T. Baumeister III, eds.), 9th Ed., Section 4.2,
McGraw-Hill, New York.
1I. Weast, R. C., ed. (1986). Handbook a/Chemistry and Physics 67th Ed., CRC Press, Boca Raton,
Florida, Section C.
Chapter 2

Physiological Hazards

There are several mechanisms by which contact of cryogenic fluids with a person
can present a physiological hazard. The most obvious of these mechanisms is that
the low temperature can cause freezing ofliving tissue. Also, in the case of cryogens
other than oxygen, the large expansion that occurs upon evaporation and warming
to ambient temperature can result in dilution of the oxygen in the surrounding
atmosphere to the point where it cannot support life. In the case of a few cryogens,
toxicity can also be a problem, but, fortunately, these are not frequently encountered.

2.1. COLD DAMAGE TO LIVING TISSUE

The low temperature of cryogens can cause serious damage to living organ-
isms. The injury can be immediate in the case of direct contact with a cold fluid or
with equipment that has been cooled to cryogenic temperature. In addition, the more
gradual cooling that may be caused by being subjected to a very cold atmosphere
for an extended period of time can also cause physical harm by inducing hypother-
mia.

2.1.1. Freezing of Tissue


Direct contact with cryogenic fluids (liquid or cold gas) or cold equipment can
cause serious damage to living tissue. Although cellular changes start to occur at
tissue temperatures as high as 15C, the formation of ice crystals in the tissue does
not occur until the tissue is cooled to about -3 C because of the freezing-point
lowering caused by dissolved solutes. 1 When the tissue temperature is low enough,
ice crystals begin to form outside of the cell walls. Water is then transferred from
the inside of the cell, through the cell wall, resulting in cell dehydration and cell
damage similar to that caused by thermal burns. For this reason, the tissue damage
caused by freezing is sometimes referred to as a "cryogenic bum" as well as
"frostbite." Further cell damage can occur as cells are deformed by ice crystals and
osmotic pressure. As the tissue temperature is lowered, the decreased blood flow
9
10 Chapter 2

can result in tissue necrosis and, possibly, gangrene. I However, records of such
damage show that tissue injury as a result of cryogen spills is rare. 2
Although numerous lecturers have demonstrated that a very brief contact with
liquid nitrogen, for example, does not necessarily cause any harm to the skin, such
a practice is not recommended by anyone without a great deal of experience in the
handling of cryogenic fluids. It is true that for very brief periods (one or two
seconds) of gentle contact (no rapid flow) with small quantities, the liquid nitrogen
does not directly contact the tissue because of the large temperature difference
between the skin and the fluid. This temperature difference causes the formation of
a gas film, and heat transfer to the skin occurs in the film-boiling regime, where the
heat transfer is somewhat slower. However, in spite of this apparent protection,
prolonging the contact any longer than a second or two can be sufficient to produce
serious tissue freezing. If the fluid (either liquid or cold gas) is traveling with a
significant velocity, freezing can occur almost immediately. Another way in which
freezing can be almost instantaneous is by contact with uninsulated, cold metal or
other cold equipment. In this case, there is no formation of a gas film between the
cold metal surface and the skin, and the heat transfer is much more rapid.

2.1.2. Hypothermia
In a case where prolonged exposure to a very large spill could occur, lowering
of the body temperature is a serious possibility. Body temperature is a function of
the production of heat within the body and the heat loss from the body. Body heat
is produced by metabolism, muscle activity, and shivering. When the body is
incapable of producing heat at a rate equal to the rate of heat removal, hypothermia
results. At a body core temperature below 35C (95 OF), generalized organ
dysfunction and central nervous system, cardiac, and respiratory depression occur.
At a lowering of the body core temperature below 28 C (82 OF), ventricular
fibrillation becomes more likely? Thus, even a minor decrease in body core
temperature is serious, and the consequences become more drastic as the lowering
of the temperature progresses.

2.1.3. Prevention of Cold Damage to Tissue


To prevent cold damage to living tissue, it is necessary to prevent contact of
the tissue with either cold fluids or cold equipment. Protective clothing should be
worn when working with cryogens. This includes safety goggles or full face shields
because the eyes are especially sensitive to the cold damage. Exposed flesh should
also be protected. Because the hands are one of the more vulnerable areas in the
transfer of cryogenic fluids, one should wear loose-fitting gloves that can be easily
removed. The gloves should not be fitted with gauntlets in which liquid could
collect. In some previous publications both leather and asbestos were recom-
mended, 2 but because of other (noncryogenic) concerns about the use of asbestos,
Physiological Hazards 11

that material should not be used. Leather gloves are good, but when they are to be
used for handling oxygen, the tanning oils should be washed out with a suitable
solvent before use. Long trousers, without cuffs, should be worn outside the shoes,
again to avoid the possibility of pooling cold liquid. Open or porous shoes should
not be worn.
The hazard of tissue freezing must also be considered in system design in the
location of vents and equipment that could become cold. All system vents must be
oriented so that venting fluids, either liquid or cold gas, cannot impinge on any part
of the body of either a worker or anyone else nearby. All vent pipes or other
equipment that could be cooled to cryogenic temperatures must be externally
insulated in any location where they could be inadvertently touched.
The onset of hypothermia is a slower process than the potential damage that
could be caused by the direct freezing of tissue. For this reason, hypothermia is less
likely except in cases where the egress from a spill area is blocked or if a person
should be rendered unconscious or immobile by other consequences of an accident
resulting in a large cryogen spill. Therefore, where such an occurrence could be
possible, it is necessary to ensure that more than one escape route is available and
that no one is allowed to work without the presence of or surveillance by another
person who could assist if necessary.

2.1.4. Treatment of Cold Damage


If, in spite of these precautions, cryogenic frostbite should occur, immediate
attention is required. The frozen tissue is painless and may appear waxy and white
or mottled blue. The frozen part may range from rock solid to firm, feel cold, and
lack sensibility. 1 After thawing, the tissue will become swollen and painful and will
be susceptible to infection. The injured person must be removed from the cold
source, and the affected part should be warmed to its normal temperature. Any
covering clothing that could restrict circulation to the injured area should be
carefully removed, taking care that skin is not removed with it. The injured part of
the body should be immersed in or gently flushed with warm water at a temperature
of 40-42 C (104-108 OF). 1,4 The water should not be hotter than 44 C (111 OF).
Safety showers or eye-wash fountains should not be used because they will
probably be at an incorrect temperature, and the flow rate of the water might be
sufficiently high to further damage the frozen tissue. The frozen part should not be
subjected to rapid streams of water, nor rubbed or massaged, either before or after
rewarming. Cold water, ice, or snow should not be applied because they could
aggravate the injury. In order to avoid any decrease in blood supply to the injured
part, the patient should not smoke or drink alcohol. 5 The patient should be kept
warm and at rest, and frozen parts should be covered with dry, sterile dressings that
are sufficiently loose to prevent any restriction of blood circulation. Warm drinks
and food may be taken by the patient. Prompt medical treatment is necessary as
12 Chapter 2

well as follow-up attention because tissue necrosis can be progressive and infec-
tious complications can develop later.
If there has been a massive exposure so that the entire body temperature is
lowered, hypothermia is a possibility. The symptoms of mild hypothermia include
apathy, confusion, lethargy, fatigue, forgetfulness, incoordination, shivering,
slurred speech, withdrawal, and increased pulse and respiratory rates. With progres-
sively deepening hypothermia, the shivering stops, and the pulse rate, blood
pressure, and respiratory rate are decreased. 3 Rewarming can be by immersion in
a warm water bath; also, treatment for shock may be necessary. The patient should
be treated extremely gently, made as comfortable as possible, and immediately
transported to the nearest hospital emergency room. In all cases of cryogenic
exposure, medical attention should be obtained as soon as possible.

2.2. ASPHYXIATION

As seen from Table 1.1, a large expansion takes place upon the evaporation of
a cryogenic fluid. An additional expansion occurs upon the gas warming to ambient
temperature. There is some variation from one cryogen to the next in the actual
volume ratios to be expected; however, for rule-of-thumb estimates, a factor of 1000
is frequently used as the ratio of the volume of the gas formed at ambient
temperature and standard atmospheric pressure to the volume of the same mass of
cryogen as a liquid. Consequently, the spill of a large quantity of a cryogen in a
confined space can lead to an atmosphere that does not support life.
When working with a cryogenic liquid in a closed room, it is necessary to
determine the maximum quantity of liquid that could be released under any
circumstance and to estimate the maximum depletion of the oxygen in the room
that could occur as a consequence of that release. For example, the instantaneous
spill of a common-size Dewar of liquid nitrogen (160 liters) in a laboratory with
dimensions of 5 m by 7 m by 3 m high would produce sufficient ambient-tempera-
ture gas to completely replace the entire room atmosphere, thus rendering the local
atmosphere totally inert and incapable of supporting life. If the spill were to take
place slowly, it is possible that the evolved gas would thoroughly mix with the room
atmosphere, with the result that the equilibrium mixture would be expelled from
the room. This complete mixing would result in a lesser decrease in the room's
oxygen content. However, without additional ventilation, even in this case the
oxygen content would decrease to less than 8%, still creating a lethal atmosphere
(see Table 2.1). If the cryogen's release or spill rate can be predicted and complete
mixing could be assumed, a ventilation rate that would prevent the oxygen content
of the room's atmosphere from becoming dangerously low could be calculated.
However, if the ventilation rate is not sufficient to thoroughly mix the atmosphere
at all points in the room, pockets of lethal atmosphere can still exist. Calculations
of this kind can be used to set a limit on the quantity ofliquid nitrogen in a specific
Physiological Hazards 13

Table 2.1. Symptoms of Oxygen Deficiency (Anoxia)a

% Oxygen at
I atm total pressureb At-rest symptoms
15-19 Decreased ability to perform tasks; may induce early symptoms in persons
with heart, lung, or circulatory problems
12-15 Respiration deeper, pulse faster, poor coordination
10-12 Giddiness, poor judgment, lips slightly blue
8-10 Nausea, vomiting, unconsciousness, ashen face, fainting, mental failure
6-8 Death in 8 min; after 6 min 50% die and 50% recover with treatment, 100%
recover with treatment in 4-5 min.
4 Coma in 40 seconds, convulsions, respiration ceases, death

a Ref. 6.
b In this table and elsewhere in this book, unless indicated otherwise, gas concentration percentages and ppm values
are on a volume or mole basis.

laboratory space and also serve as a guide to determine the necessary safety
precautions that must be taken, such as limiting access of personnel, requiring
continuous oxygen monitoring, or providing external venting of the equipment.
Closed volumes, such as tanks, are obviously dangerous to enter, even if they
have not seen cryogenic service. These volumes should be entered only with
extreme caution. The entire procedure should be carefully planned in advance with
attention being given to ways to ensure that the atmosphere is breathable and that,
if necessary, rescue is possible without endangering additional people. The tank
must first be warmed to ambient temperature. Typical precautions that can then be
taken include the disconnecting of all attached pipelines and providing a continuous
supply offresh air forced into the tank with the input air on one end of the tank and
the exhaust at the other end (care must be taken to avoid dead ends where a
nonbreathable atmosphere could still exist). Analysis of the tank's atmosphere may
be necessary, and voice or visual communication with anyone inside the tank is
desirable. Also, the rescue procedure should be decided before tank entry. It must
be remembered that a filter respirator is of no value in protecting against asphyxi-
ation. The entire procedure should be discussed with and approved by knowledge-
able safety personnel. Following a written procedure is advisable.
Even outdoors, the vapors from most evaporated cryogens, which are still cold,
can linger in low spots and present a hazard. If there is any doubt about the oxygen
content of the atmosphere in an area near where a cryogenic fluid has been
evaporating, personnel should not be allowed to enter the area without self-con-
tained breathing apparatus unless a test with an oxygen analyzer shows that the
atmosphere is safe. It must also be remembered that the gas evolved is not
necessarily uniformly distributed around the area where a spill has occurred.
Diffusion and convection currents are powerful dispersing forces. However, in the
absence of convection currents caused either by wind (outdoors) or ventilation
14 Chapter 2

(indoors), buoyancy can be more powerful than diffusion, and the degree of oxygen
depletion can then vary from one place to another. The vapors of a cryogen at its
normal boiling point will be negatively buoyant and could be expected to accumu-
late near the floor level. However, for hydrogen and helium, if the vapors are
quickly warmed, or if ambient-temperature gas is vented into the enclosure, the
oxygen depletion could be more serious in the higher portions of the room.
In the case of sudden or acute asphyxia, such as would occur from inhaling a
gas with very little or no oxygen content, unconsciousness is almost immediate. In
this situation a person can fall in a few seconds and can die within a few minutes
if prompt treatment is not obtained. In one such situation, one man entered a tank
and dropped unconscious within just a few breaths. A second man then entered the
tank to rescue him and also dropped unconscious. Then there were two people to
rescue. Unfortunately, the rescue efforts were not in time to save the first man.
Gradual asphyxia can occur if the oxygen content of the atmosphere is
gradually or only partially reduced. Any reduction in the normal oxygen content of
the breathable atmosphere is undesirable, but the lower the oxygen concentration,
the more dangerous is the hazard. Table 2.1 describes some ofthe consequences of
subjecting a person to a reduction of oxygen in the atmosphere.
Another insidious aspect about anoxia is that the victim is frequently unaware
of any danger. In fact a feeling of euphoria can set in, during which a potential
victim would be unaware of any danger and make no attempt to rescue himself.
One of the authors (FJE) is personally aware of an incident that occurred during
physiological training in which several people were placed in a large tank in which
the atmospheric pressure was reduced to simulate a high altitude. The simulated
altitude was such that the oxygen partial pressure in the tank's atmosphere was less
than the sum of the carbon dioxide pressure plus the water vapor pressure in the
lungs. Thus, it was necessary to breathe through an oxygen mask. To demonstrate
the hazard of anoxia, one man was asked to remove his mask and then identify red
or black playing cards while the man at his side faced the cards, one by one. After
about 15 seconds, the first man started to make mistakes in the identification. After
about 25 seconds, he stopped paying any attention to the task at hand and was
content to sit there with a smile on his face. His mask was quickly replaced, and he
suffered no ill effects. However, had the mask not been replaced, he would have
been content to sit there and die.
Table 2.1 shows the seriousness of oxygen deficiency. Furthermore, the results
shown are for working at one standard atmosphere (sea level). At a higher elevation,
the total atmospheric pressure will be reduced, oxygen supply will be at a lower
total pressure, and the hazard of oxygen deficiency will become more serious. Also,
if the diluent gas is carbon dioxide (C02), concentrations of CO 2 as high as 9%
(reducing the oxygen content to 19%) can only be tolerated for a few minutes at
most. At this CO 2 concentration, the body cannot rid itself of the CO 2 produced in
normal respiration.?
Physiological Hazards 15

2.3. TOXICITY

Most of the commonly handled cryogenic fluids are not toxic. However, ozone
(0 3), carbon monoxide (CO), and fluorine (F 2) are highly toxic and must be treated
with caution.
Carbon dioxide is usually not considered a cryogen, nor is it truly toxic.
However, for completeness, it will be discussed briefly here because of its common
usage. As discussed in Section 2.2, CO2 in small amounts has no deleterious effects
on the human body. However, CO 2 is the product of respiration, and excess
quantities must be removed from the lungs as they are formed in the body and
delivered to the lungs by the blood circulation system. A prolonged exposure to a
concentration of? .6% CO2 can produce headaches, dizziness, and sweating, and at
a concentration 10% or higher, unconsciousness can occur in less than one minute.
Prolonged exposure to CO2 at this concentration can be fatal. Impairment in
performance has been noted in prolonged exposure at CO 2 percentages as low as
3%. The Occupational Safety and Health Administration (OSHA) has established
an upper permissible limit of 5000 ppm (or 0.5%) for CO 2 exposure in an 8-hour
day. A short-term exposure limit (no more than 10 minutes) of 30,000 ppm (3%)
has been recommended. 8 First aid for a person suffering from overexposure is to
remove the person from the CO2 atmosphere (making sure that the necessary safety
precautions have been made for the rescuer). Ifbreathing has ceased, then artificial
respiration should be applied. The patient should be kept warm, and immediate
medical attention should be sought.
Ozone, the most reactive form of oxygen, is blue in the liquid form. Besides
being extremely toxic, 0 3 also presents an explosive hazard (see Section 9.7).03
is produced continuously in the outer layers of the atmosphere by the action of solar
ultraviolet radiation on the oxygen in the air. The concentration of 0 3 varies, but at
sea level it can be present to the extent of about 0.05 ppm. 9 At a concentration of
0.015 ppm, it has a barely detectable odor, and in concentrations as low as 1 ppm,
0 3 is a strong irritantto the respiratory system and eyes. 10 For the exposure of human
beings, the maximum permissible 0 3 concentration is 0.1 ppm, and 50-60 ppm is
presumed to be immediately fatal. First aid for 0 3 exposure consists of removal
from exposure, and, for severe cases, oxygen should be administered, and medical
attention should be sought. II
Carbon monoxide presents a hazard by inhalation. Chemical asphyxia occurs
because CO has an affinity to combine with the hemoglobin in the blood that is 300
times as great as that of oxygen. 12 By combining with the hemoglobin, CO renders
the blood incapable of carrying the needed oxygen to body tissues. At a concentra-
tion of 600 ppm, toxic symptoms will occur after an exposure of about one hour.
At 1000-2000 ppm, slight heart palpitations can occur in about one half-hour, and
headache and nausea in about two hours. Inhalation of a concentration of 4000 ppm
(0.4%) can be fatal in less than one hour. 13 The maximum permissible exposure
16 Chapter 2

limit of a worker during an 8-hour day or a 40-hour work week is 35 ppm. A person
suffering from CO exposure should first be removed from the contaminated
atmosphere and kept warm (making sure that the rescuer is not jeopardized by doing
so). If the patient is unconscious, he/she should be placed on one side. If the patient
is breathing, oxygen should be administered. If the patient is not breathing, artificial
respiration should be given along with administering oxygen. In either case, prompt
medical attention should be obtained.
With fluorine there can be a hazard either from inhalation or from contact with
the skin. All organic materials are extremely reactive with fluorine. At as Iowa
concentration as 50 ppm, breathing can be impossible without respiratory equip-
ment, and at 100 ppm skin irritation occurs. Fluorine has a sharp, penetrating odor
that makes the inhalation of toxic quantities unlikely, unless the individual is
trapped in an exposed area. Fluorine odor can be detected at concentrations down
to about 0.14 ppm. Thus, the nose is an effective and reliable fluorine detector. 2 If
fluorine odor is detected, personnel should leave the area, moving cross wind until
clear of the contaminated area. An individual who has been exposed to a toxic
fluorine atmosphere should be removed from that area and immediately deluged
with water. Contaminated clothing should be removed. Water flushing should be
continued for 15 to 20 minutes. A fluorine bum should be treated as a combination
chemical and thermal bum, and prompt medical attention should be obtained. 2 The
time-weighted average exposure limit for an 8-hour day or a 40-hour week is 1 ppm.
The short-term exposure limit ( 15 minutes) is 2 ppm. 14

REFERENCES
1. Gonzalez, F., and Walton, R. L. (1991). Cold-induced tissue injuries, in The Clinical Practice of
Emergency Medicine (A. Harwood-Nuss, C. H. Linden, R. C. Luten, G. Sternbach, and A. B.
Wolfson, eds.), Chap. 199,1. B. Lippincott Co., Philadelphia, Pennsylvania.
2. Ordin, P. M. (1983). Safety, in Liquid Cryogens (K. D. Williamson, Jr. and F. J. Edeskuty, eds.),
Vol. I, Chap. I, pp. I-57, CRC Press, Boca Raton, Florida.
3. Klainer, P. (1991). Hypothermia, in The Clinical Practice ofEmergency Medicine (A. Harwood-
Nuss, C. H. Linden, R. C. Luten, G. Sternbach, and A. B. Wolfson, eds.), Chap. 200, J. B. Lippincott
Co., Philadelphia, Pennsylvania.
4. Meryman, H. T. (1957). Physiol. Rev. 37,233.
5. Washburn, B. (1962). N. Engl. J. Med. 266,974.
6. Compressed Gas Association (1992). Oxygen Deficient Atmospheres (Less than 19.5%), Com-
pressed Gas Association Bulletin CGA SB-2, Arlington, Virginia.
7. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
8. Compressed Gas Association (1984). Carbon Dioxide, Compressed Gas Association Bulletin CGA
G-6, Arlington, Virginia.
9. Kaye, S. M. (1978). Encyclopedia ofExplosives and Related Items, PATR2700, Vol. 8, U.S. Army
Armament Research and Development Command, Dover, New Jersey.
10. Lewis, R. J., Sr. (1992). Sax sDangerous Properties ofIndustrial Materials, 8th Ed., Van Nostrand
Reinhold, New York.
Physiological Hazards 17

II. Gatwood, G. T., and Murphy, G. F. (1969). Safety in the chemical laboratory: Ozone hazards, J.
Chern. Educ. 46(2), AI03.
12. Compressed Gas Association (1989). Safe Handling of Liquid Carbon Monoxide, Compressed
Gas Association Bulletin CGA-P-13, Arlington, Virginia.
13. Schmauch, G. (1972). Liquid carbon monoxide: Market grows, Cryogenics and Industrial Gases
1972 (July/August), 19.
14. American Conference ofIndustrial Hygienists (1992). 1992-1993 Threshold Limit Values for
Chemical Substances and Physical Agents and Biological Exposure Indices, American Conference
of Governmental Industrial Hygienists, Cincinnati, Ohio.
Chapter 3

Embrittlement of Materials

In general, materials tend to increase in strength as their temperature is lowered.


The deformation of metals occurs with the movement of crystal-lattice dislocations.
As the temperature is raised, the thermal energy of the vibrating atoms assists this
movement. Hence, as the temperature is lowered, the decreased thermal vibration
of the metal lattice adds to the strength of the material. l However, in the design of
cryogenic equipment it is usually best to use the ambient-temperature strength
because of temperature gradients that might exist within the equipment and also
because cryogenic equipment frequently must operate at warmer temperatures.
This increase in strength as the temperature is lowered does not make all
materials satisfactory for use in cryogenic applications. If structural materials lose
ductility or become brittle, they can break suddenly and unexpectedly under normal
stress conditions. Depending upon the circumstances, such a failure can be cata-
strophic. There are two processes by which structural materials can become brittle
in cryogenic service: low-temperature embrittlement and, if in hydrogen service,
hydrogen embrittlement.

3.1. LOW-TEMPERATURE EMBRITTLEMENT

Some structural materials undergo a change from ductile to brittle behavior as


the temperature is lowered. The temperature at which the ductility disappears is
called the nil-ductility temperature. This temperature is different for different
materials and can be considerably higher than cryogenic temperatures. Cold em-
brittlement has caused the breakup of ships in cold ocean water. 2 Several failures
of storage tanks have also been blamed on this phenomenon. Tank failures have
occurred at higher than cryogenic temperatures. However, an example that did
involve cryogenic temperature and that is of particular interest in regard to cryo-
genic safety is the failure that occurred in a cylindrical tank containing liquefied
natural gas (LNG) in Cleveland in 1944. The tank, with a volume of 4250 m3
(150,000 ft3), was fabricated of a steel containing 3.5% Ni (by weight). This
material has been shown to have too low a ductility for application at LNG
19
20 Chapter 3

temperature (about 110 K). The tank ruptured, spilling its contents. Because there
was not sufficient diking or channeling to control the spread of the spilled LNG,
approximately 4165 m 3 (147,000 ft3) of LNG spread rapidly over a wide area. There
were ignition sources within the spill area, and the subsequent fire damaged the
support system of an adjacent LNG spherical storage tank with a capacity of
2350 m 3 (83,000 ft3) so that it also spilled its contents. The spilled LNG entered
the sewer system and exploded there. The external flame reached a height of850 m
(2800 ft), and damage occurred up to 400 m (~mile) away. The death toll was 128,
and over 200 injuries were reported. Property damage was estimated at $6,800,000.
This accident set the LNG industry back several decades. 3
The strength of a structural material is usually determined by a test in which
a specimen (usually a round bar) is placed in tension. As the tension is increased,
the bar is stretched or strained. In the initial part of the test, the strain is proportional
to the stress, and if the stress is removed, the bar essentially returns to its original
dimensions. In this portion of the test, the specimen is referred to as being elastic.
If the material has some ductility, and ifthe applied stress is sufficiently great, there
is ,a departure from linearity, with the strain increasing more rapidly than is the case
for the initial linear relationship. At this point the bar will retain a permanent
elongation and will no longer return to its original length when the stress is released.
At some small, but arbitrary, amount of permanent deformation (frequently 0.2%),
the applied stress is defined as the yield stress. As the stress is further increased, the
elongation increases, and the permanent stretching of the bar also increases.

Ultimate Stress - - - = - -__

Rupture Rupture

I
I
I
I
I
I
I
I
-oj 10--0.2% Strain

Fig. 3.1. Typical stress-strain diagram for ductile and brittle materials,
Embrittlement of Materials 21

Eventually, a maximum stress is reached, and the bar begins to "neck down,"
causing an apparent decrease in the stress, and finally the specimen breaks. The
maximum stress is called the tensile or ultimate stress. A brittle material, on the
other hand, does not exhibit this yielding, and consequently no permanent defor-
mation is evidenced prior to rupture. Rather, upon reaching the ultimate strength,
the specimen abruptly breaks. This is a more hazardous behavior for a material in
use under stress. If operating stress in a ductile material should slightly exceed the
yield stress, the member can yield and relieve the stress while remaining intact. A
brittle material in the same circumstance can fracture without warning. Figure 3.1
illustrates the results of the tensile tests of ductile and brittle materials.
A test that is frequently applied to a material to determine its ductility is the
Charpy impact test. This test is performed on a notched bar with a rectangular cross
section. A weight on a pendulum is then allowed to strike the specimen and break

160

140

120
V
/
/
E
~1oo
i
~
CiS 80

//
1ic.. .f2\.
..
e:
III
or;
60
()

~r.

-
40

--
w--:-
-~

20
po--
/ 8?:
./ ..:z.-
o
o 50 100 150 200 250 300 350
Temperature (K)
Fig. 3.2. Charpy impact strength as a function of temperature for various materials. 4 (I) 9% nickel
steel, (2) 304 stainless steel, (3) Cl020 carbon steel, (4) beryllium-copper, (5) K-Monel, (6) titanium,
(7) 2024-T4 aluminum.
22 Chapter 3

it. The energy needed to break the specimen is a measure of the ductility of the
material. The results ofthis test, conducted over a range of temperatures extending
down to the lowest temperature of use, indicates the effect on ductility oflowering
the temperature. Figure 3.2 shows the effect of temperature on Charpy impact
values for several materials. From tensile tests, a measure of ductility can also be
obtained from the reduction in area at the location of the fracture, as well as from
the total elongation of the specimen. The rate at which the ductility decreases with
temperature, as shown by any of these parameters, is an important consideration
and can be used for guidance in material selection. Charpy impact values of
20.3 N'm (15 ftlb), or greater, have been considered acceptable. Unfortunately,
there is no direct way to relate the Charpy impact value, or these other indications
of ductility, to a safe operating stress for the material. 2 Thus, for accurate design of
cryogenic vessels, the more sophisticated techniques of fracture mechanics, applied

450

400 r\
350 ~
300 ~ ........
~ Tensile -

--
150
Yield
100

50

o
o 50 100 150 200 250 300
Temperature (I<)

Fig. 3.3. Yield and tensile stress of 5086 aluminum as a function oftemperature. 5
Embrittlement of Materials 23

to data taken on the material under consideration, should be used to determine safe
operating stresses.
Another insight into the ductile or brittle behavior of a material can be gained
from the examination of a plot, for a given material, of the tensile and yield strengths
as a function of temperature. In general, both of these strengths increase as
temperature is lowered. However, the rate of increase can lead to an understanding
ofthe change in ductility of the material being tested. Figure 3.3 shows the behavior
of 5086 aluminum, a material satisfactory for cryogenic service. The figure shows
that the tensile strength increases faster than does the yield strength as temperature
is lowered. The distance between the two curves is an indication of the ductility of the
material. As shown in Fig. 3.3, this distance increases as the temperature is lowered.
This type of behavior indicates that the material is becoming more ductile as the
temperature is lowered. Figure 3.4 shows the different behavior of AISI 430 stainless
steel. Here it is seen that the two curves approach each other at liquid-nitrogen

----
700

600 "- r--


""- .............

K
500

"""'" ~
~

"" --
"iU 4OO
a..
~

~
Ci5300
~eld

r----
200

100

o
o 50 100 150 200 250 300
Temperature (K)

Fig. 3.4. Yield and tensile stress of AISI 430 stainless steel as a function oftemperature. 5
24 Chapter 3

Table 3.1. Embrittlement of Structural Materials at Low Temperature Q

Materials Behavior at low temperature


Copper, nickel, all copper-nickel alloys, alumi- Remain ductile at low temperature if ductile at
num and all its alloys, austenitic stainless room temperature
steels with> 7% nickel, zirconium, titanium,
most fcc metals, b polytetrafluoroethylene
Iron, carbon steel and low-alloy steels, molybde- Become brittle at low temperature
num, niobium, zinc, most bcc metals,b most
plastics

a Ref. 6.
b fcc and bcc refer, respectively, to face-centered cubic and body-centered cubic crystal structures.

temperature (77 K), and thus the material becomes more brittle as the temperature
is lowered. Hence, AISI 430 is not a satisfactory material for cryogenic service. 5
Metals that are used successfully at cryogenic temperatures include aluminum
and its alloys, copper and its alloys, nickel and some of its alloys, and austenitic
stainless steels. In general, these are all metals with a face-centered cubic (fcc)
crystal structure. However, unstabilized austenitic stainless steel (some of the 300
series) can revert to a martensitic structure when stressed above the yield stress at
low temperature. Presence of the martensite structure reduces the ductility of the
metal. Table 3.1 lists some metals that are suitable for cryogenic service, as well as
some that are not.

3.2. HYDROGEN EMBRITTLEMENT

Hydrogen can effect profound, deleterious changes in the physical properties


of metals. This effect is termed hydrogen embrittlement (HE) and was recognized
as early as 1875. 7 By the early 1940s, hundreds of papers had been written on the
subject, and by 1960 the volume ofliterature on the subject was overwhelming. In
the study of the mechanism(s) of HE, the large number of pertinent variables
presents a formidable list to be accounted for by any theory of embrittlement. This
list includes such factors as time of exposure to hydrogen, stress state, pressure,
temperature, hydrogen concentration, physical and mechanical properties of the
metal, microstructure, surface conditions, diffusion rates, purity of the hydrogen,
and the nature of the crack front. HE has been divided into three classes: hydrogen
reaction embrittlement, internal hydrogen embrittlement, and environmental hy-
drogen embrittlement. Table 3.2 presents some characteristics of these forms of HE.

3.2.1. Hydrogen Reaction Embrittlement


Hydrogen reaction embrittlement is a chemical phenomenon that occurs more
readily at elevated temperatures. In this case the hydrogen chemically combines
Embrittlement of Materials 25

Table 3.2. Characteristics of Hydrogen Embrittlement"

Environmental Internal hydrogen Hydrogen reaction


Characteristic hydrogen embrittlement embrittlement embrittlement
Usual source of Gaseous hydrogen Processing, electrolysis, Gaseous or atomic
hydrogen corrosion hydrogen from any
source
Typical conditions 10...{i_l08 Pa H2 0.1-10 ppm average H Heat treatment or
pressure. Most severe content. Most severe service in hydrogen,
near room near room usually at elevated
temperature. temperature. temperatures
Observed from Observed from
-100C to 700 C. -100C to +100 C.
Gas purity is Strain rate is
important. Strain rate important.
is important.
Test methods Notched tensile, Notched failure, slow Can be observed
unnotched tensile, strain rate tensile, visually or
creep rupture, bend tests metallographically
fatigue, fracture
toughness, disk
pressure test
Crack initiation Surface or internal Internal crack initiation, Usually internal
initiation incubation initiation from
(reversible), slow bubbles or flakes
discontinuous
growth, fast fracture
Rate-controlling step Adsorption is transfer Lattice diffusion to Chemical reaction to
step, absorption or internal stress raisers form hydrides or gas
lattice diffusion is bubbles
embrittling step.

a Ref. 8.

with one or more of the constituents of the metal. An example would be the
combination of hydrogen with carbon to form methane gas or with oxygen to form
water vapor, which could then form blisters in the metal and weaken it. If the
reaction is with the base metal or any of its alloying elements, the resulting solid
hydrides are usually very brittle and also have a lower density than the parent metal.
Thus, additional stress is induced by the expansion of the hydride that was formed
and then confined within the metal. 9

3.2.2. Internal Hydrogen Embrittlement


Internal hydrogen embrittlement and environmental hydrogen embrittlement
differ in the way the hydrogen enters the metal. In the former case, the hydrogen is
introduced in the processing of the metal. This can occur in anyone of several ways.
26 Chapter 3

Iron or aluminum can react with water to produce a metal oxide and liberate
hydrogen. Acid cleaning, electroplating, or other finishing operations are also
sources of hydrogen. Internal hydrogen embrittlement has been the cause of
structural failures in members that presumably have not experienced hydrogen in
their use. Industry has experienced hydrogen embrittlement problems in high-hard-
ness springs, bolts, lock washers, valve and compressor parts, and gauges, particu-
larly when the parts have been electroplated. Delayed failure has been observed in
aircraft landing gear struts containing hydrogen that was introduced during the
processing of the metal. In some cases, collapse occurred while the aircraft was at
rest on the ground after successfully withstanding several hard landings. 9

3.2.3. Environmental Hydrogen Embrittlement


Environmental hydrogen embrittlement may occur when the material is sub-
jected to a hydrogen atmosphere. A pressure intensifier that had been used to pump
nitrogen and oil to 400 MPa failed quickly at 300 MPa when used to pump
hydrogen. 10 Failure has occurred in the gauge tube ofbourdon gauges in hydrogen
service at a pressure only a fraction of that offull scale. I I Several failures have been
experienced in tanks storing hydrogen at 35 MPa (5000 pSi)12 while similar tanks
operated at 24 MPa (3500 psi) were apparently not affected. In the 1960s and 1970s,
hydrogen tube trailers in Germany experienced about 70 failures. 9
HE can arise when hydrogen is present in quantities greater than the amount
that can be taken up by its solubility in the metal. Since metals with body-centered
cubic (bcc) and hexagonal close-packed (hcp) crystal structures have lower solu-
bility for hydrogen than do those with fcc crystal structures, hydrogen embrittle-

Table 3.3. Effect of Hydrogen Exposure on Ultimate Strengtha

Material (notched sample) Exposure (at 80 OF) Strength [MPa (psi)]


4140 (low strength) 69 MPaN2 1660 (241,000)
41 MPaH2 1427 (207,000)
69 MPaH2 1407 (204,000)
4140 (high strength) 69 MPaN2 2496 (362,000)
14MPaH2 931 (135,000)
41 MPaH2 834 (121,000)
C1025 69 MPaN2 730 (106,000)
69 MPaH2 552 ( 80,000)
KMonelPH 69 MPaN2 1731 (251,000)
69 MPaH2 779 (113,000)
K Monel (annealed) 69 MPaN2 993 (144,000)
69 MPaHz 724 (105,000)

a Ref. 13.
Embrittlement of Materials 27

ment is more serious with bcc and hcp metals. Also, as a rule of thumb, a metal in a
high-strength condition is more susceptible to HE than the same metal in an annealed
condition. This effect is shown in Table 3.3, which reports the results of ultimate tensile
tests on several metals, in different strength conditions, tested after having been
subjected to either hydrogen or nitrogen pressure. For the 4140 steel the decrease in
tensile strength was about 15% in the low-strength condition, whereas in the
high-strength condition the strength decreased by about a factor of3. 13
Although HE has been observed over a somewhat wider range of temperature,
for many metals and alloys the effect of internal and environmental HE maximizes
between -100C and + 100 C.12 Thus, both internal and environmental HE show
the greatest effect around room temperature (200-300 K). Measurements of plastic
strain illustrate this behavior (see Fig. 3.5), showing that the effect of HE decreases

1.0+-------.r-1--~==::::+_~----+_-____::;;;.:..::....__1

0.8+-----+---\-~--l~---_d.........,,:::::::::::===-_l

:8111
~ 0.6+------+------1r----t-------+-+------1
iiI
~
~
a:: 0.4+------+-------'\----t--------.4--------1

0.2-t------+---------'t.:------:~----1-----__I

O.O+---.....----+----.---+----,.---+---,------l
o 100 200 300 400
Temperature (K)

Fig. 3.5. Effect oftest temperature on susceptibility to hydrogen embrittlement. 14 The plots of strain
ratio (hydrogen test/air test) vs. test temperature show ductility minima in three Fe-Cr-Ni alloys charged
with deuterium for three weeks at 69 MPa and 620 K.
28 Chapter 3

as the temperature is lowered and disappears in the range of cryogenic tempera-


tures. I4 However, cryogenic equipment usually will experience room temperature
during its service, and thus HE becomes a concern if the equipment is to experience
a hydrogen atmosphere.

3.2.4. Hydrogen Embrittlement Mechanisms


A number of mechanisms for HE have been advanced during the long period
of its investigation. I 5-I? Several of these theories remain viable and can be sup-
ported by experimental and theoretical evidence. It is believed that several mecha-
nisms contribute to HE and can exist within a given material simultaneously and
that no single theory can explain all of the hydrogen degradation phenomena that
have been observed. I5 Three of these mechanisms are hydrogen-related phase
changes, hydrogen-enhanced plasticity-related fracture, and decohesion. I6
The hydrogen-related phase changes can occur with the formation of hydrides
or martensitic phases within the metal. The new phases can be brittle and may be
stabilized by the presence of hydrogen and the stress at crack tips, thus embrittling
the material.
Although hydrogen-enhanced local plasticity would seem to be incompatible
with a brittle failure, the distribution of hydrogen within a stressed material is highly
nonuniform. Consequently, a locally increased plasticity in places such as at a crack
tip causes a local deformation that can lead to a failure in which the overall or
macroscopic deformation is very small, which would indicate a brittle failure.
The decohesion effect of HE is one ofthe earliest of the proposed mechanisms
of HE. In this case HE is presumed to be caused by a decrease in atomic bonding
strength resulting from the local hydrogen concentration. Thus, the material can
fracture when the stress exceeds the "cohesive stress," a property that is assumed
to be lowered by the presence of hydrogen.
One or more of the above theories of HE can be used to explain the following
phenomena. The susceptibility of a metal to HE is strongly dependent upon the
composition of the metal and also its metallurgical history. II These factors affect
the ability of the hydrogen to migrate within the metal. The hydrogen can be
adsorbed on the metal surface and then travel through the body of the metal as
atomic hydrogen. Upon reaching a microcrack, or void, it can then recombine to
form molecular hydrogen, and the resulting hydrogen pressure adds to the local
stress in the metal. The local stress may favor the formation of a hydride with one
of the constituents of the parent metal. In addition to the consequences of the first
two mechanisms mentioned above, if the resulting hydride has a lower density than the
parent metal, the confinement of the hydride can also add to the local stress pattern.
HE is attributed to high, localized hydrogen concentrations. Such concentra-
tions can be caused by stress-enhanced diffusion rates of absorbed hydrogen to
lattice defects and reaction sites. Thus, HE is aided by high applied or residual
Embrittlement of Materials 29

stresses and sharp notches. The embrittlement manifests itself in crack formation
requiring an incubation period. If the hydrogen can be removed before the initiation
of this crack formation, the effect of HE can be reversed. 9
The yielding ofthe metal can be an important factor in inducing the results of
HE. Walter and Chandler I 8 have shown that in the storage vessel materials that they
tested, the strength of unnotched specimens was not affected whereas the ductility
was greatly reduced. They also considered plastic strain an important factor that
can lead to premature failure by hydrogen embrittlement. 18 In the cases of pressure
vessels that have experienced failure, the failure has frequently been in the area of
welds where residual stresses could have been a factor, again pointing to plastic
strain as a factor in causing failure by HE.

3.2.5. Avoiding Hydrogen Embrittlement


The statement has been made that almost any metal can be embrittled by
hydrogen if the conditions are strong enough. Yet, the experience of hydrogen
shipment and distribution in steel cylinders (K bottles) has been both successful
and safe. The technology of handling hydrogen, both as a high-pressure gas and as
a liquid, has an enviable safety record. 9 Possibly this might be attributed to luck.
However, it is much more likely that the use of conservative design stresses to avoid
any plastic strain and scheduled retesting are responsible for this good record.
Consideration of HE should be included in the design of cryogenic equipment
and in the selection of material that could experience hydrogen. Thin stainless-steel
liners have been used in pressure vessels and piping. Weep holes can be provided
in the structural member to vent the hydrogen that could diffuse through the liner.
Some success has been achieved in using aluminum, copper, silver, gold, or oxide
coatings to prevent hydrogen's access to the pipe or vessel walls. The stress to which
the metal is subjected is a very important parameter to consider in avoiding HE.
Avoidance of yielding of the metal experiencing a hydrogen atmosphere is very
important. Welds have been found to be significant sites for failure. The heat-
affected zone frequently produces hard spots, residual stresses, and a microstructure
conducive to embrittlement. Incomplete fusion, inclusions, and voids caused by
improper welding procedures provide sites for subsequent embrittlement. Welding
fluxes can also provide sources of hydrogen.9 Some of the materials that have
served well for hydrogen usage are also acceptable materials for cryogenic-
temperature service. Table 3.4 presents a listing of some materials in the order of
their decreasing susceptibility to HE. However, a thorough study of currently
available information on the effect of hydrogen on construction materials is
recommended for the selection of materials for use in a system that will contain
hydrogen. For critical locations, testing of the actual material to be used is a good
idea. References 15-17 are excellent sources for more detailed, basic information
on HE.
30 Chapter 3

Table 3.4. Metals and Alloys Embrittled by Hydrogena (Listed in Order of Decreasing
Susceptibility at Room Temperature)

Environmental hydrogen Internal hydrogen Hydrogen reaction


embrittlement embrittlement embrittlement
High-strength steels High-strength steels Hydrides (MHx)
18Ni maraging, 401, 440C, 4340,4140, H-ll, AM355, H reacts with matrix Ti, Zr, Hf,
430F, 403, 431, H-ll, 4140, 18Ni maraging, E8740, 17- V, Nb, Ta, Mn, Ni, Pd, U, Pu,
1042 (Q&T), Fe-9Ni--4Co, 4PH,17-7PH Th, rare earths
17-7 PH
Nickel and nickel alloys Experimental Fe-Ni-Cr alloys Alkalis
Electroformed nickel
Nickel (200, 270, 301) Experimental Fe-Cu alloys
Inconel (625, 700, 706, 718, X),
Rene41, Hastelloy x, Udi-
ment 700, Waspaloy, INI00,
MARM-200DC
Low-strength steels Ii, Zr, V, Nb, Ta, Cr, Mo, W, H reacts with elements in MgZr,
Co, Ni, Pt, Cu, Au, AI, Mg, MgThalloys
Armco iron, CK22, CK45,
and/or some of their alloys High-pressure gas bubbles (H
1020, 1042 Nor., HY-80, HY-
100, A-302, A-515, A-517, A- forms H2) steels
5338, 1146a, HY-130,
SA-105
TItanium alloys Metastable stainless steels H reacts with foreign elements
304L,310 in matrix to form:
Ti-6AI-4V, Ti-5AI-2.5Sn CH4 in low-alloy steels and
Molybdenum-TZM Ni alloys
H20 in welded steels and Cu,
Cobalt alloys
Ni,Ag,
HS-188, L-605, S-816 NH3 in molybdenum
Metastable stainless steels High-strength nickel alloys
304L, 305, 310, 309S Inconel 718, Rene 41,
Waspalloy, Hastelloy x
K Monel, Be-Cu alloy 25, pure
titanium Stable austenitic steels
316, A-286, U-212, 21-6-9
Stable stainless steels
316,321,347, A-286,
Armco 21-6-9, 22-13-5
Copper alloys, OFHC Cu
TD-Ni, TD-NiCr
Magnesium alloy HM21A
Aluminum alloys
1100,2219,6061,7039,7075

a Ref. 9.
Embrittlement of Materials 31

REFERENCES
1. Rosenberg, H. M. (1971). The behavior of materials at low temperature, in Advanced Cryogenics
(C. A. Bailey, ed.), Chap. 3, Plenum Press, London.
2. Wigley, D. A., and Halford, P. (1971). Construction materials and fabrication techniques, in
Cryogenic Fundamentals (G. G. Haselden, ed.), Chap. 6, Academic Press, New York.
3. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
4. Durham, T. F., McClintock, R. M., and Reed, R. P. (1962). Cryogenic Materials Data Handbook,
Office of Technical Services, Washington, D.C.
5. McClintock, R. M., and Gibbons, H. P. (1960). Mechanical Properties of Structural Materials at
Low Temperatures, a Compilation from the Literature, National Bureau of Standards Monograph
13, U.S. Department of Commerce, Washington, D.C.
6. Timmerhaus, K. D., and Flynn, T. M. (1989). Cryogenic Process Engineering, Plenum Press, New
York.
7. Johnson, W. H. (1875). On some remarkable changes produced in iron and steel by the action of
hydrogen and acids, Proc. R. Soc. London 23, 168.
8. Gray, H. R. (1974). Testing for hydrogen enviromnent embrittlement: Experimental variables, in
Hydrogen Embrittlement Testing, ASTM STP-543, American Society for Testing and Materials,
Philadelphia, Pennsylvania.
9. Edeskuty, F. J., et al., (1979). Critical Review and Assessment of Enviromnental and Safety
Problems in Hydrogen Energy Systems, Los Alamos Scientific Laboratory Report LA-7820-PR,
Los Alamos, New Mexico.
10. Dodge, B. F. (1953). High pressure research in the chemical engineering department of Yale
University, Trans. ASME 75, 331.
II. Mills, R. L., and Edeskuty, F. J. (1956). Chem. Eng. Prog. 52(11),477.
12. Swisher, J. H., Keaton, S. C., West, A. J., and Jones, A. T. (1974). Survey of Hydrogen
Compatibility Problems in Energy Storage and Energy Transmission Systems, Sandia Laborato-
ries Energy Report SAND74-82 19, Albuquerque, New Mexico.
13. Cavett, R. H., and Van Ness, H. C. (1963). Embrittlement of steel by high pressure hydrogen gas,
Weld. Res. Supple. 1963 (July), 316s.
14. Caskey, G. R., Jr. (1983). Hydrogen Compatibility Handbook for Stainless Steels, E.!. du Pont de
Nemours & Co. Report DP-I643, Savannah River Laboratory, Aiken, South Carolina.
IS. Hirth, J. P. (1984). Theories of hydrogen induced cracking of steels, in Hydrogen Embrittlement
and Stress Corrosion Cracking (R. Gibala and R. F. Hehemann, eds.), American Society for Metals,
Metal Park, Ohio.
16. Birnbaum, H. K. (1990). Mechanisms of hydrogen-related fracture of metals, in Environment-
Induced Cracking ofMetals (R. P. Gangloffand M. B. Ives, eds.), NACE-l 0, National Association
ofCoITosion Engineers, Houston, Texas.
17. Oriani, R. A., Hirth, J. P., and Smialowski, M., eds. (1985). Hydrogen Degradation of Ferrous
Alloys, Noyes Publications, Park Ridge, New Jersey.
18. Walter, R. J., and Chandler, W. T. (1968). Effects of high pressure hydrogen on storage vessel
materials, Proceedings of the ASM Westec Conference, March 11-14, 1968, Los Angeles,
American Society of Metals, Metals Park, Ohio.
Chapter 4

Stresses Caused by Thermal Contraction

Although there are exceptions over limited temperature ranges, materials generally
have positive thermal expansion coefficients. Usually, the temperature change from
ambient to cryogenic temperature will amount to as much as 200 K (360 OF) or
greater. This large temperature decrease will cause a significant thermal contraction
in any material being cooled from ambient temperature to cryogenic temperature.
However, the thermal expansion coefficient is also a function of temperature,
decreasing as the temperature is lowered. Figure 4.1 shows the temperature depend-
ence of the thermal expansion coefficient of copper.! Although there is still further
contraction below the temperature ofliquid nitrogen, usually over 90% ofthe total
contraction from room temperature to any lower temperature will have already
taken place at 77 K because of the decrease in the thermal expansion coefficient for
many materials with temperature. Consequently, in cooling from ambient tempera-
ture to any cryogenic temperature, there will be a thermal contraction of about 0.3%
in iron-based alloys, over 0.4% in aluminum, and well over I % in many plastics.
The first two of these figures give useful rule-of-thumb values for quick estimates.
The more accurate values needed for system design can be obtained from published
tables of integrated thermal contraction over the temperature range of interest.
Tables 4.1 and 4.2 give some representative examples? Figure 4.2 shows the total
integrated thermal contraction from ambient temperature down to any cryogenic
temperature for several materials. 3

4.1. STRESSES CAUSED BY DIMENSIONAL CHANGE


(STEADY-STATE TEMPERATURE)

The thermal contraction of the parts of a cryogenic system that will be cooled,
and thus will experience these typically large temperature changes, must be
considered in the design of the system. If the system design does not accommodate
this contraction, large thermal stresses can result. As an example, consider the
contraction of a 304 stainless steel rod or pipe, firmly fastened at each end and not
allowed to contract while it is being cooled from ambient temperature to the
33
34 Chapter 4

Table 4.1. Integrated Thermal Expansion of Some MetalsD

Integrated thermal expansionb

1020 low 304 Free


Temp carbon stainless machining
(K) eu Ni Al Mg Zn Ti steel steel Monel Inconel yellow brass
0 0 0 0 0 0 0 0 0 0 0 0
20 0 0 0 0 0 -1.1 0 0 0
40 2 I 2 5 9 I I -1.5 -1.5 I 4
60 10 4 10 12 28 2 4 2.8 6 5 15
80 25 12 24 29 57 6 10 14 15 12 34
100 44 23 46 55 93 14 20 30 29 24 57
120 67 38 72 87 133 24 32 50 45 38 85
140 92 55 104 124 176 35 47 73 64 55 115
160 119 74 138 164 221 47 63 97 85 74 146
180 148 95 175 208 267 60 81 124 107 95 180
200 178 117 214 254 314 74 101 151 130 117 214
220 209 140 255 303 363 89 121 180 155 140 249
240 240 164 297 353 413 105 142 210 180 163 285
260 272 188 341 403 465 121 164 241 207 187 322
280 305 213 385 453 518 138 187 272 234 212 359
300 339 239 431 503 572 155 210 304 261 238 397

a Ref. 2.
b Thermal expansion = MILo x 105 (Lo = length at 0 K).

temperature ofliquid nitrogen (77 K). The elastic modulus, E, is defined as the ratio
of the stress, a, to the strain, E, of an elastic specimen:

E = alE or a=EE

where E will be in the same units as a (commonly psi) because E is the ratio of a
change in dimension to that dimension and is thus without units. E does not vary
greatly as the temperature is reduced into the cryogenic temperature range. Increases
are in the range of 5-20% as the temperature is lowered from 300 K to 0 K. For 304
stainless steel we can use an average value for E of 180,000 MPa (26.1 x 106 psi) and
an integrated thermal contraction of 0.3% (0.003). The resulting stress can be seen
to be about 540 MPa (78,000 psi). This is well above the allowable stress and,
depending upon the metallurgical condition, can be above the yield stress of 304
stainless steel. Such stresses are usually not tolerable and might result in broken
pipes, leakage of fluid, or damage to the pipe restraints. The allowable design stress
is listed for a number of materials in the ASME Pressure Vessel Code, Section VIII
(1983), and the values for some common construction materials4 are given in Table
4.3.
Thermal Contraction 35

1.8x1 0-5

1.6><10-5
L.-----
~
1.4x10-5
/
/
I
/
/
/
II
/
o
)
o 50 100 150 200 250 300
Temperature (I<)

Fig.4.1. Thennal expansion coefficient [(l/L)(dL/d1)] of copper as a function of temperature. I

It might be possible to use Invar piping without provision for its thermal
contraction because its thermal expansion coefficient is about one-sixth that of
stainless steel, and its elastic modulus is only about two-thirds that of stainless steel.
The resulting stress in this case should be well under the allowable stresses.
However, detailed design calculations must be made to determine that adjacent
parts of the system are not damaged by such an arrangement.
36 Chapter 4

4.1.1. Storage and Transport Vessels


In most cryogenic equipment, stresses like that mentioned above cannot be
tolerated. In the case of vacuum-jacketed storage or transport vessels (or Dewars),
the inner shell can undergo its contraction freely if the suspension system and

2.0+---~~---+----+----1-----I~-----1

l1.5
~ Nylon

;a
~

C
.12
~
1:
8
11.0
CD
~
GI
CD
c::
::J
S
~

0.5
I minum

50 100 150 200 250 300


Temperature (K)

Fig. 4.2. Plots of linear thermal contraction of some common materials as a function of temperature,3
showing the total contraction at a given temperature as the temperature is lowered from 300 K to that
temperature. PTFE =Polytetrafluoroethylene.
Thermal Contraction 37

Table 4.2. Integrated Thermal Expansion of Some Plasticsa

Integrated thennal expansionb.c

Temp PE rod, glass Cast Cast epoxy Nylon


(K) fiber filled phenolic rod polymer rod FTH PSd PTFEd Pyrex'

0 0 0 0 0 0 0 0 0
20 3 14 10 10 21 27 45 -1
40 11 38 39 37 65 82 115 -2
60 21 70 78 81 116 152 200 -1.5
80 34 109 126 142 173 235 300
100 49 154 181 217 235 329 410 4.5
120 67 205 242 301 301 432 525 8.5
140 88 261 310 393 372 542 650 13
160 110 321 385 493 444 658 785 17.5
180 134 385 467 600 531 778 940 22.5
200 159 452 556 716 618 900 1130 27.5
220 184 524 651 841 711 1024 1370 33
240 210 602 753 977 811 1152 1620 39
260 237 688 862 1124 921 1284 1875 44.5
280 264 782 980 1282 1045 1422 2130 50.5
300 291 889 1107 1450 1187 1566 2695 57

a Ref. 2.
b Thermal expansion = MiLo x 105 (Lo = length at 0 K).
C Abbreviations for materials: PE, polyester; FTH, fluorothene; PS, polystyrene; PTFE, polytetrafluoroethylene.

d Specimen taken parallel to the rod extrusion direction.

e Calculated from data for Si02 and B201.

interconnecting piping will not be overstressed. Numerous cycles of contraction to


operating temperature and subsequent wanning to ambient temperature (and con-
sequent expansion) can occur in the lifetime of the vessel. Therefore, the suspension
system and interconnecting piping must be designed to accommodate the change
in dimension of the inner shell and the cyclic stresses encountered in the lifetime
of the vessel.
In the simplest vessel design, all tubes and instrumentation enter through the
top closure flange, and the inner shell support consists only of a neck tube for
vertical support and perhaps some side bumpers or a snubber at the bottom for
lateral support. The neck tube will have a temperature distribution that varies
between constant ambient temperature (when the vessel is empty) and a thennal
gradient that goes from the temperature of the cryogenic liquid at the lower end to
38 Cbapter4

Table 4.3. Allowable Stress for Materials at


Room Temperature or Lower" (ASME Pressure
Vessel Code, Section VHI, 1983)

Allowable stress
Material [MPa (psi)]
Carbon steel (outer shell only)
SA-285 Grade C 94.8 (13,750)
SA-299 129.2 (18,750)
SA-442 Grade 55 94.8 (13,750)
SA-516 Grade 60 103.2 (15,000)
Low-alloy steel
SA-202 Grade B 146.5 (21,250)
SA-353B (9% Ni) 163.7 (23,750)
SA-203 Grade E 120.6 (17,500)
Stainless steel
SA-240 (304) 129.2 (18,750)
SA-240 (304L) 120.6 (17,500)
SA-240 (316) 129.2 (18,750)
Aluminum
SB-209 (1100-0) 16.2 (2,350)
SB-209 (3004-0) 37.9 (5,500)
SB-209 (5083-0) 68.9 (10,000)
SB-209 (6061-T4) 41.4 (6,000)
Copper
SB-11 46.2 (6,700)
SB-169 (annealed) 86.2 (12,500)
Nickel alloys (annealed)
SB-127 (Monel) 128.2 (18,600)
SB-168 137.9 (20,000)

a Ref. 4.

near-ambient temperature at the top (when the vessel contains a cryogen). The space
between the inner and outer shell must be sufficient so that the inner shell is free to
rise when the neck tube contracts or shortens. Also, if a gap occurs between the side
bumpers and the inner shell when the vessel is cooled to operating temperature, this
gap must be sufficiently small that any possible sideways motion of the inner shell
does not overstress the neck tube or its joints.
For many cryostats and for large storage and large transport vessels, the design
can be more complicated. Usually, internal piping must connect to the inner shell
and then exit the vacuum space in such a way as to provide continuous or
Thermal Contraction 39

overlapping vacuum insulation spaces from the Dewar to the transfer line. The
piping must have a sufficiently circuitous routing through the Dewar's vacuum
space to provide an effective thermal barrier to heat leak and to prevent overstress
in the piping, the inner shell, or the piping connections during thermal cycling of
the Dewar.
The insulation system is also an integral part of the Dewar design. Usually,
thermal stresses are not a problem in the smaller-sized Dewars that are convention-
ally used in laboratories (typically under one cubic meter in volume). Larger
Dewars (hundreds of cubic meters in volume) are usually fabricated with a carbon
steel outer shell (this shell remains at ambient temperature) and a stainless steel or
aluminum inner shell. Many of these vessels are field-fabricated, and the inner
surface of the outer shell and the outer surface of the inner shell cannot easily be
made to have a low emissivity. The radiation transport of heat from the ambient-
temperature outer shell to the inner shell at cryogenic temperature is an important
consideration in the design of a Dewar.
For small Dewars (a few liters), the radiation heat transport can be minimized
by silvering or polishing the above-mentioned surfaces to produce emissivities of
about 1-2%. For larger Dewars (and also newer smaller Dewars), the use of
multilayer insulation, consisting of numerous layers of reflective foils, serves the
same purpose. Either of these insulation methods requires a relatively high vacuum
(absolute pressure of 0.013 Pa or W-4 Torr or better) to decrease the in-leakage of
heat by convection or residual gas conduction.
For very large Dewars (tens to hundreds of cubic meters in volume), an
alternate insulation system involves the filling ofthe annular space between the two
shells with perlite powder. The powder serves two purposes: the reflective particles
decrease the radiation transport of heat, and the many tiny spaces between the
particles minimize the convection transport of heat so that the vacuum requirements
are much less demanding (1.3 Pa or 10-2 Torr). Also, the perlite powder is relatively
inexpensive. The evacuated-powder insulation method is mainly used in larger
vessels where it is easier to provide relatively thick insulation spaces, typically
about one meter in thickness.
A problem that has arisen with evacuated-perlite insulation systems is the
shifting of the powder upon thermal cycling of the Dewar. Upon the initial filling,
the powder is uniformly distributed in the annular space between the two shells.
When the inner shell is cooled to operating temperature, the thermal contraction
can produce a void under the inner shell. During the time that the Dewar contains
cryogenic liquid, this gap can be partially or completely filled as some ofthe perlite
falls down into the gap beneath the inner shell. When the Dewar eventually becomes
empty and is left to warm up to ambient temperature, either to be serviced or because
it is not necessary to keep it filled, the inner shell will expand to its original size,
and the excess perlite underneath the inner shell will not flow up to its former
position. Thus, an upward force can be imposed upon the inner shell and on its
40 Chapter 4

Gap Formed Upon


Cool-down to
Operating Temperature

~""-- ~~Dewar Inner Shell, Cold


,---.".
" ~" , , - Dewar Inner Shell, Warm

- . - Perlite

- . - Dewar Outer Shell

Fig. 4.3. Perlite compaction mechanism. 5 Perlite can fall into the gap caused by the thennal contraction
of the inner shell but cannot be squeezed out upon subsequent wanning. Thus, stress can build up.

support system. The same phenomenon can also occur at the ends of horizontal,
cylindrical vessels. Ifthe Dewar is unsymmetrically supported, longitudinal forces
can also develop. This phenomenon has been called "perlite compaction." Figure
4.3 illustrates the perlite compaction problem in the vertical plane. 5
The perlite compaction problem has several solutions. One solution is to apply,
to the outer surface of the inner shell, a soft, flexible bat (glass wool or rock wool)
that either can be squeezed or can expand to fill the gap. Then the perlite powder
is filled into the remaining annular space. Another solution is to design the support
rod system to accommodate the motion of the inner shell without building up any
stress. A way to do this would be to have the vertical support rods pass through a
horizontal pad welded to the outer surface of the inner shell so that the weight of
the inner shell rests on a nut on the underside of the pad. In this way the inner shell
will be free to rise if it experiences an upward force when expanding against the
perlite powder and can descend onto the pad again upon recooling. With either of
these solutions, the flexibility of the piping in the annulus must be sufficient to
accommodate the motion of the inner shell.
The inner-shell motion caused by perlite shifting has been known to break
support rods and crack the bellows between the inner and outer shell of a horizontal
cylindrical Dewar that contained a manway for entry to the Dewar's interior. The
crack then caused a leak from the manway into the annular space and destroyed the
operating vacuum. Figure 4.4 shows the way in which the problem arose in the
horizontal vessel. From Fig. 4.4 it can be seen that the Dewar had one fixed support
and one sliding support to accommodate the longitudinal contraction and expansion
that occurs during temperature cycling. Because the internal piping was to exit the
inner shell on the end of the Dewar closest to the fixed support, it was necessary to
have a thicker insulation space on this end. On the other end, where the contraction
of the inner shell is the greater, the insulation space was thinner. This caused the
buildup of unequal longitudinal stresses (the largest buildup of perlite occurring in
Thermal Contraction 41

Evacuated Vacuum
Perlite Jacket

Fig.4.4. Schematic of Dewar damage by perlite compaction. Maximum contraction of the inner shell
occurs at the greater distance from the fixed support. In this case the same end also has the smaller
thickness of perlite. Perlite can fill in the end gaps formed upon cool-down. Upon subsequent warming,
because of the greater amount of perlite that was shifted and the smaller total thickness, the greater stress
will occur in the thinner perlite layer, causing a resultant force to the left.

the thinnest amount of perlite), with the result that the inner shell was forced toward
the end with the thickest layer of perlite. After a few temperature cycles the vacuum
deteriorated, and when the upper manhole cover was removed, the lower end of the
bellows was seen to have had its lower end, where it entered the inner shell,
displaced about 30 nun. Further inspection also revealed that support rods on the
fixed ends were broken off. In this case the solution to the problem was to place a
sliding cap, connected to the outer shell and fitting snugly over the end of the inner
shell nearest the sliding support. In this manner, the inner cylinder could contract
and slide within the cover, but the sliding cover could prevent the perlite powder
from entering the gap that would be formed upon cooling the inner shell. In
perlite-insulated cryogen-storage Dewars it is advisable to monitor the vacuum in
the insulation space periodically and also to look for unexpected frost spots.

4.1.2. Transfer Lines and Piping Systems


Transfer lines for cryogenic fluids must also provide for the thermal contrac-
tion of the line while it contains liquid or cold gas. For short-distance transfers, a
meter or so, liquid nitrogen and higher-boiling cryogens are frequently transferred
in single lines with an externally applied insulation, such as any of various foams
or rock wool. For the lower-boiling cryogens, particularly liquid hydrogen and
liquid helium, and for longer distance transfer of any cryogen, it is usually necessary
to use vacuum-jacketed transfer lines. In this case, provision must also be made to
allow the vacuum jacket to conform to any changes in position of the inner line,
42 Chapter 4

without contact between the two concentric lines and without the buildup of any
undue stresses.
The contraction (shortening) of the inner line can be accommodated in one of
two ways. The first, and most commonly used, is the practice of designing the line
to have sufficient flexibility so that it can be distorted into a slightly different
position without causing a large stress. The flexibility is provided by including
elbows and "U" bends in the line. The alternative would be to use expansion bellows
in the line. Although possible, there are several disadvantages to the use of
expansion bellows in the inner tube of a transfer line. First, the bellows connections
are a possible source of future leakage, and if a leak were to occur, finding the leak
and repairing it would be considerably more difficult. Second, the motion allowed
by the expansion of the bellows is also a function of the pressure in the line. Thus,
to prevent unwanted contact between the two concentric lines, additional spacers
would be needed, with greater strength, and consequently more heat leak into the
cryogen space. Third, the expansion bellows constitutes a significant source of
pressure drop during fluid transfer.
The calculation for providing flexibility in a straight line with one "U" bend
has been described by Barron.4 Figure 4.5 shows a line with a "U" bend and gives
the definition of the line dimensions, W, H, and Lp ' so that the maximum stress,
Smax, can be calculated from Eq. (4.1). We can define a = W/Lp, ~ = H/Lp, and Et as
the integrated thermal contraction per unit length from ambient temperature to the
cryogenic temperature of interest (see Table 4.1). Then:

fora ~~, and

for a < ~, where E is the elastic modulus (Young's modulus), Do is the outside
diameter of the line, and

B = (2 ~/3) [~(2 +~) +3 a (I-a) + (3/8)(1 + 2 ~)(DjH)2] (4.3)

Each term in these equations is unitless. Hence, any consistent set of units can be
used.
For more complicated line routings, computer solutions are usually used, and
several versions are available, even for personal computers. The output usually
includes a diagram of the system indicating pipe locations and will show the
movement to be expected in cooling from ambient temperature to the final cryo-
genic condition. Stresses and moments are computed and can be tabulated for each
pipe section andjoint. The dotted line in Fig. 4.5 illustrates the final position of the
piping system after being cooled from ambient temperature to the operating,
cryogenic temperature.
r
Thermal Contraction 43

:, - ----\ I/D""".'D - SHAPE H

,-
_-' ,,\__ l

A --- -~ ,-- --- -~

~~.~ ~I
Fig. 4.5. Original and defonned (after cooling to operating temperature) shapes of a "U" bend in a
cryogenic fluid transfer line.

The vacuum j acket must also comply with the motion of the inner line in such
a way as to prevent unwanted contact between the two concentric lines and undue
buildup of stress in that line. This is usually achieved by placing expansion bellows
on the outer line, which also accommodates ambient-temperature changes.

4.2. STRESSES CAUSED BY THERMAL GRADIENTS

Some components of a cryogenic system, such as support rods of the inner


shell of a Dewar, must maintain a thermal gradient, even at steady state. However,
most of the components that will be cooled to cryogenic temperature will experi-
ence thermal gradients only during the cool-down phase of operation. Theoretically,
the same gradients could exist during the rewarming to ambient temperature.
However, the warming process is usually much slower, and large thermal gradients
are not so likely to occur.
The stresses resulting from strong thermal gradients will depend upon the rate
of cooling, the thermal conductivity of the material, and the thickness of material
being cooled. An unfavorable combination of these parameters can result in
overstressing of the material and presumably could lead to rupture in some cases.
Figure 4.6 shows the results of some calculations made for the cool-down of
a 203-mm-inside-diameter (nominal 8-inch, schedule 40) stainless-steel flange. In
the figure, the flange is shown as split along a radius, and graphs of the temperature
gradient and consequent stress are shown between the split sections. Note that for
this flange the web thickness is 114 mm (4.5 in.). The flange was assumed to be
cooled by a flow of liquid hydrogen, and when the inner bore of the flange had
cooled to a temperature of228 K, the outer surface was still at its original, ambient
44 Chapter 4

r- ,
300
290 V
LEGEND:
g280
V ,"
----Realistic Temperature ~ 270 / ,
Gradient ~ II ,
- - - - - - Linear Temperature i260
E250
/
,
Gradient
~24O /,
230
220

300
'i 250
~ 200
:z 150 .\
~ 100 \
iii 50 ,
~CD 0
I\,'
E -SO I'--. ' ,
,
~ -100
,
6 -150
80 100 120 140 160 180 200 220

Fig. 4.6. Dependence of stress upon the thermal gradient in a thick flange being cooled by flowing
liquid hydrogen. The dashed lines are for a linear thermal gradient, and the solid lines are for a more
realistic thermal gradient. The shaded area represents the flange; it has been opened up to insert the
graphs of temperature and stress.
Thermal Contraction 45

temperature of 300 K. In this condition the outside of the flange will be in


compression, and the inside in tension. If one were to assume that there would be
a linear thermal gradient, a probably tolerable maximum stress of about 186 MPa
(27,000 psi) would result. This is illustrated by the dashed lines in Fig. 4.6.
However, the thermal gradient cannot be linear for two reasons. First, the thermal
conductivity decreases with a decrease in temperature, and this will cause the
temperature gradient to be concave-downward. Second, in traversing from the outer
surface to the inner surface, the cross-sectional area for heat transfer is also
decreasing, and this also will cause an additional deviation from linearity in the
same direction. The resulting thermal gradient and stress are shown in Fig. 4.6 by
the solid lines. In this case the maximum stress (tensile) is almost 276 MPa
(40,000 psi), which is certainly above the allowable stress and may be above the
yield point of the material.
The rate of cooling is one of the important parameters in the generation of
thermal stress that can be controlled by operating procedures. Usually, cryogenic
components such as transfer lines are cooled from ambient to operating tempera-
tures with a flow of the fluid tobe transferred. For the lower-boiling cryogens,
precooling with liquid nitrogen is occasionally performed, but, in either case, there
is a large temperature difference between the coolant and the line at the beginning
of the cooling. The only operational parameter available to control the rate of
cooling is the flow rate of the cooling fluid. The faster the flow of fluid, the greater
will be the quantity of coolant passing a given cross section of the pipe, and also
the greater will be the heat-transfer coefficient. Consequently, the more rapidly will
the cooling proceed. N ovak6 has made calculations of maximum flow rates of either
liquid nitrogen or liquid hydrogen being used to cool either austenitic stainless steel
or aluminum piping, and some of the results are shown in Fig. 4.7. In order to make
this type of calculation, one must make a number of assumptions, including the
method of calculation ofthe heat-transfer coefficient and the maximum stress to be
used. The calculations were made for Fig. 4.7 by assuming that the heat-transfer
coefficient from the pipe wall to the coolant is calculated from the Dittus-Boelter
equation7 and the maximum stress is the allowable stress (see Table 4.3). Cooling
rates can be controlled either by regulating the pressure in the supply Dewar or by
the valve opening at the inlet or outlet of the line.
There is another concern in the cool-down of long, horizontal transfer lines.
During much of the time that the cooling fluid is flowing, the flow will be in the
two-phase flow regime. Figure 4.8 shows a snapshot view of an intermediate
portion of the line at a time during the cool-down process when the first part of the
line has been cooled almost to the temperature of the cryogen. This portion of the
line is filled with flowing liquid. Further downstream, where the line is somewhat
warmer, the heat transfer will be sufficient to produce two-phase flow. Further yet
downstream, all of the liquid will have evaporated, and cold gas will cool the line
and in tum be warmed to ambient temperature before exiting the end of the line.
46 Chapter 4
10~--------------------.- __________________ ~

Aluminum, LN2

~
E 0.1 T--------''''''''~--t_""""~---------_I

Stainless Steel, LN2


0.01 +----------.:::........:::---+--------___--/

Stainless Steel, LH2


O.OOl~----~~--~~~~~~~----~--~ __~~~~_u
0.1 1 10
t lDi (anIcm)
Fig. 4.7. Maximum cool-down flow rates ofliquid nitrogen (LN2) and liquid hydrogen (LH2) to keep
thennal stresses below maximum allowable stress for a pipe. Wmax is the maximum flow rate, t is the
pipe waH thickness, and Di is the inside diameter of the pipe.6

The actual cool-down process, with its pressure and flow surges, is much more
chaotic than Fig. 4.8 suggests. However, the overall process does proceed as
described. During the cooling process, the local behavior as shown proceeds down
the line. Therefore, the exiting gas will remain relatively warm during most ofthe
cool-down process and will then rapidly decrease in temperature as the liquid front
approaches, just before liquid issues forth from the end ofthe line and the cool-down
is complete. (At locations in the line where thicker wall members, such as flanges,
are present, the cooling will be slower and some two-phase flow can persist.) The
concern during this process is with the two-phase portion shown in Fig. 4.8.
Two-phase flow can occur in a number of different ways (see Fig. 4.9). Most of
these flow types are not of concern. However, the occurrence of the stratified and
wave flow regimes can give rise to a situation in which, at a given cross section,
Thermal Contraction 47

FLOW .....
00

300

g
I-

20

Fig. 4.8. Cool-down model, representing the average behavior of a typical section of a long cryogenic
transfer line during the cool-down process. 8

~~~r-----~-~
PLUG STRATIFIED WAVE

~a-+--
_ ~
J.! - -
- ~I--~::::.~II:
~:-:!.1
SLUG ANNULAR DISPERSED
(almost aU liquid)

1111-BUBBLE
Fig. 4.9. Two-phase flow regimes. 9
48 Chapter 4

the bottom of the pipe (cooled by liquid) can cool faster than the top (cooled by
gas). If this were to occur to any great degree, the bottom of the pipe will try to
contract faster than the top, and the pipe will bow upward in the middle. This can
lead to unwanted stresses in the pipe as well as in its supports. 8
Baker9 has given a correlation that predicts the type of two-phase flow that
will occur under various conditions. The correlation is presented in Fig. 4.10. The
important parameters are the mass flow per unit area of liquid, L B, and of gas, GB

105 -r--------~--------~--------~_r------~------__,

Dispersed

Wave
Bubble or Froth

i ............ .. ..

20.7 kPa (gage) Dewar PreSsure

Stratified

1~~-------+------~r-------r-------~~----~

Fig. 4.10. Baker's correlation,9 showing the type of two-phase flow to be expected under various
conditions. GB, gas mass flow rate [lbml(ft2.hr)]; LB, liquid mass flow rate [lbm/(ft2 hr)]; y, liquid surface
tension (dyne/cm); !iL, liquid viscosity (cp); pG, gas density (Ibmlft\ PL, liquid density (Ibmlft\ A =
[(pa/0.075)(prl62.3)]112; 'P = (73/Y)[(!iL(62.3/pd]1I2. The operating lines for the cooling process with
Dewar supply pressures of 103.4 kPa and 20.7 kPa show that raising the supply pressure results in faster
flow, consequently causing more of the cool-down process to occur before crossing into the stratified
or wave flow regimes.
Thermal Contraction 49

(defined in the caption to Fig. 4.10). The density of the gas and liquid phases and
the viscosity and surface tension of the liquid are the pertinent fluid properties. The
properties of the liquid and gas phases are compared to those of air and water, the
values for which are already contained in Baker's definitions of A and 'P. The Baker
plot is presented on a log-log basis; therefore, the entire evaporation process cannot
be represented on it. This is because the sum of LB plus GB must equal the total
mass flow, m. As the evaporation takes place, GB will vary from 0 initially to m
when all the liquid is evaporated, whereas LB will vary from m to O. Consequently,
the start and end of the evaporation process will always lie off the graph. However,
the process can be followed from, say, I % to 99% evaporation. If the corresponding
points for different degrees of evaporation are placed on the Baker plot, a prediction
of the type of two-phase flow at each point is possible. Note that increasing the flow
rate raises the locus of these points on the Baker plot, thus effectively moving more
of the vaporization process above the wave and stratified flow regimes. By
increasing the flow rate and consequently moving the locus of these points upward
on the Baker plot, most of the vaporization process can be made to take place in
one or more of the more favorable flow regimes. Although this method of analysis
has not been widely tested, the flows observed have fit the expected pattern in the
few cases in which it has been tested with liquid hydrogen and liquid nitrogen. In
one case with liquid nitrogen, where the flow was below the recommended
minimum flow rate, a one-ton vessel was lifted off the floor by the vacuum-jacketed
supply and return lines. These lines were 203 mm in inside diameter (nominal
8-inch schedule 40 stainless-steel pipe). To show conditions under which about
95% of the evaporation process can occur without entering the wave or stratified
flow regimes, calculations were made that give suggested minimum flow rates as
a function of pipe inside diameter for liquid oxygen, nitrogen, and hydrogen. to The
results are presented in Fig. 4.11.
The previous discussion presented reasons for not exceeding a maximum flow
and corresponding rate of cool-down of a cryogenic pipeline. For a long, horizontal
transfer line, it is also desirable to keep the cool-down flow above a lower limit to
avoid the bowing of the pipeline. It is possible that for a long horizontal line with
very thick flanges, these two flow rate limits would coalesce, or even overlap, thus
apparently precluding the cool-down of the line by flowing the cryogenic liquid
through it. If that case were ever to arise, the line could be cooled more slowly with
boil-off gas from the supply Dewar, thus eliminating the possibility of two-phase
flow in the line. Another possibility would be to introduce a smaller quantity of
liquid cryogen, stop the inflow, and allow the liquid to evaporate and repeat this
process over a long enough time so that only minimal temperature gradients would
exist at any time.
50 Chapter 4

100.-----------~----------_.----------_,r_--------~

50 LOX

10~----------1_------~~q_--~~----+_--------~

~
~
!
a:
1.0 -t-----;~~___l------_+_:"......=----_+-----___l
~
~ 0.5

0.1-t-~~--~--_+----------_+----------~----------~

0.05

0.01 +-..-----..--.--I---.--..-----..-+-~...___r_-.,......._+-_,_-,...___r_~
o 20 40 60 80
Pipe Inner Diameter (em)

Fig. 4.11. Minimum cool-down flow rate for nonstratified two-phase flow. 10

4.3. OTHER STRESS CONSIDERATIONS

It should be pointed out that the above considerations constitute a means of


avoiding overstress in cryogenic equipment by the use of operational limitations.
A safer procedure would be to design the equipment so that the safety of operation
would not depend upon operating parameters. The above methods can be used to
determine whether attainable flow rates and operating conditions can present a
stress problem in the equipment. If so, the redesign of the system might be able to
preclude any operating technique that could jeopardize any part of the system by
overstress. If this is not the case, safe operating procedures must be developed along
with means to ensure strict adherence to those procedures. It is also necessary to
design equipment that is sufficiently rugged to withstand any handling that can be
experienced during any part of its installation and use.
Thermal Contraction 51

It must be remembered that the cool-down of cryogenic equipment to operating


temperature is frequently accompanied by pressure and flow oscillations that can
also impose additional stresses on the system. Pressure surges during this phenome-
non can amount to several times the supply pressure entering a transfer line. During
nonflow situations, thermal acoustic oscillations can cause momentary elevated
pressures as well as pump more heat into stored cryogen. For this reason it is
necessary to exercise extreme caution in the initial operation of any cryogenic
system until the nature of these additional perturbations is well understood.

REFERENCES
I. Johnson, V. J., ed. (1960). A Compendium of the Properties of Materials at Low Temperature
(Phase I), WADD Technical Report 60-56, Part II, Properties of Solids, Office of Technical
Services, U.S. Department ofComroerce, Washington, D.C.
2. Scott, R. B. (1988). Cryogenic Engineering, Met-Chern Research, Boulder, Colorado.
3. Wigley, D. A., and Halford, P. (1971). Materials of construction and techniques offabrication, in
Cryogenic Fundamentals (G. G. Haselden, ed.), Chap. 6, Academic Press, London.
4. Barron, R. F. (1985). Cryogenic Systems, Oxford University Press, New York.
5. Edeskuty, F. J., and Williamson, K. D., Jr. (1977). Liquid hydrogen storage and transmission, in
Hydrogen: Its Technology and Implications (K. E. Cox and K. D. Williamson, Jr., eds.), Vol. II,
Chap. 3, CRC Press, Boca Raton, Florida.
6. Novak, J. K. (1970). Cool-down flow rate limits imposed by thermal stresses in liquid hydrogen
or nitrogen pipelines, in Advances in Cryogenic Engineering (K. D. Timroerhaus, 'ed.), Vol. 15,
pp. 346-353, Plenum Press, New York.
7. Dittus, F. W., and Boelter, L. M. K. (1930). University ofCalifornia Publications in Engineering,
Vol. 2, UCLA Press, Los Angeles, p. 443.
8. Bronson, J. C., Edeskuty, F. J., Fretwell, 1. H., Hammel, E. F., Keller, W. E., Meier, K. L., Schuch,
A. F., and Willis, W. L. (1960). Problems in cool-down of cryogenic systems, in Advances in
Cryogenic Engineering (K. D. Timroerhaus, ed.), Vol. 7, pp. 198-205, Plenum Press, New York.
9. Baker, O. (1954). Design of pipe lines for simultaneous flow of oil and gas, Oil Gas J. 53(July
26), 185.
10. Edeskuty, F. J., Reider, R., and Williamson, K. D., Jr. (1971). Safety, in Cryogenic Fundamentals
(G. G. Haselden, ed.), Chap. 11, Academic Press, London.
Chapter 5

Buildup of Pressure in Closed Systems

From the large volumetric ratios shown in Table 1.1, one can infer that as confined
volumes of cryogens experience heat input, which they must unless there is a source
of refrigeration, pressure can build up. Unless gas can be vented from the system,
this pressure increase will continue until eventually either liquid density at ambient
temperature is approached or the container ruptures. Starting with saturated liquid
at 1 atm, the upper pressure limits that can be attained in this manner are enormous
and, in most cases, cannot be sustained without vessel rupture. Table 5.1 presents
estimates of these pressure limits, which can only be reached if, at the start of the
confinement, the container is completely filled with the liquid phase of the cryogen.
The pressures indicated in Table 5.1 cannot be reached before vessel rupture
in transport Dewars, nor in the usual laboratory experimental cryostats. Therefore,
it is necessary, in any cryogenic system, to provide safe and reliable relief systems
in every space in which liquid cryogen or cold gas could be trapped. This includes
piping systems in which fluid could be trapped in spaces such as between two valves
in series. There are two other volumes that must be protected against pressure
buildup. One of these is a volume containing a cold gas or cryogenic liquid that is
thermally connected to, and being cooled by, a volume containing a cryogen and
where pressure could build up when the external cryogen coolant is removed, either
intentionally or by normal evaporation. The other type of volume that must be
similarly protected is the evacuated insulation space of vessels or transfer lines

Table 5.1. Maximum Pressure Buildup in Closed


Systems Filled with a Liquid CryogenQ

Maximum pressure
Cryogen [MPa (psi)]
Helium 103 (15,000)
Hydrogen 172 (25,000)
Nitrogen 296 (43,000)

Starting with vessel completely filled with liquid, no venting, and


warming to 300 K.

53
54 Chapter 5

--
VENT _ _ _ _ _ _ _ _---,

Fig. 5.1. Volumes that require pressure relief. l

containing a cryogen that is sufficiently cold to condense air. If such a space were
to have a very small leak, over a long period of time air could leak in and condense
on the cold surface of the inner vessel and exhibit essentially zero vapor pressure.
Thus, there would be no evidence of its presence. Upon removal of the cryogen,
the inner vessel will warm up, allowing the condensed air in the vacuum space to
exert its full pressure. Depending on the amount of air that had previously con-
densed, this pressure could be sufficient to rupture the vacuum j acket or to collapse
the inner vessel. For this reason the vacuum valve at the evacuation port of the
insulation space of a Dewar or cryostat is often built so that it can also provide
pressure relief if necessary. Figure 5.1 illustrates the three types of spaces that
require pressure relief systems. 1
Buildup of Pressure 55

Table 5.2. Liquid Cryogen Boil-off Rate (Heat Leak) Correction

Liquid density"
Cryogen Temperaturea (K) (gil) Vapor densitya (gil) Correction (%)
Heliwn 4.2 125 16.9 15.6
Hydrogen 20.3 70.8 1.34 1.9
Neon 27.1 1207 9.55 0.8
Nitrogen 77.3 808 4.62 0.6
Argon 87.3 1395 5.77 0.4
Oxygen 90.2 1140 4.47 0.4

a At normal boiling point.

5.1. CONSIDERATIONS IN CALCULATING THE RATE OF


PRESSURE RISE IN A CLOSED SYSTEM

In order to estimate the rate at which pressure will rise in a closed system
containing a cryogenic fluid, it is first necessary to know the rate of heat input into
the system. In the case of a Dewar, heat input is typically ascertained by measuring
the boil-off gas from the system while filled with the cryogen to be stored, once
thermal equilibrium has been established within the Dewar. For cryogens that boil
at higher temperatures, this is fairly satisfactory. However, for liquid helium, and
to a lesser extent liquid hydrogen, a correction must be applied to the value that
would be obtained by merely measuring the quantity of boil-off gas and using the
heat of vaporization to compute the heat input rate. This correction is necessary
because ofthe smaller relative difference between the density of the liquid and that
of the coexisting vapor at saturation temperature and pressure. As the liquid
evaporates, not all of the resulting vapor leaves the Dewar; some of it takes the
place of the liquid that has evaporated. For cryogens other than helium or hydrogen,
this correction amounts to less than 1%. For hydrogen and helium, the corrections
are 1.9% and 15.6%, respectively. Table 5.2 gives this correction for the most
common cryogens. For precise calculations of the heat input into a system using
the measurement of the boil-off gas quantity, these corrections should be applied
by increasing the heat input rate by the amount shown in the table.
Ifthermal equilibrium exists within the Dewar, and ifthe correct heat leak into
the Dewar is known, a calculation based upon the first law of thermodynamics can
then be used to provide an estimate of the rate at which the pressure will rise in an
unvented Dewar. The system volume and initial mass of cryogen (liquid plus vapor)
will be constant. With the known heat input rate, the total internal energy within
the closed system will be known as a function of time. These values can then be
used to compute the vapor and liquid fractions and the pressure of the system at
subsequent times. Details of the method to make such a calculation can be found
in a number of thermodynamics textbooks. 2
~

1.2,1--------,-------~--------r_------_r------_,r-------,_------_.

~ 0.8 I \ \\\ \: "k . . "" . . . . . . k .. 1 ==- I~q~


~
LL.

~
is 0.6 I II \
nan" I "\. .... k :::;::;>4.7':;::;=C I
w
Ul
~
a.
E
()
o 0.4 I "=1 ~.7 /1

0.2 I I -

0.0 I I I I 1 1 1
o 2 3 4 5 6 7 (")
Reduced Pressure, Pr ::r
=
~
..
Fig. 5.2. Generalized compressibility factor vs. reduced pressure for selected reduced temperatures. 3 Ul
Buildup of Pressure 57

At temperatures well above the critical point where only a single phase is
present, it is also possible to compute pressures by use of the gas laws. This might
be necessary if the individual gas properties are not available at the elevated
pressures that can be reached. However, it is of interest to note that for these very
high pressures, it is not possible to obtain accurate or even very close results with
the use of the ideal gas law, i.e.,

PV=nRT
where P is the pressure, V is the volume, T is the temperature, n is the number of
moles ofthe gas present, and R is the universal gas constant in units consistent with
the units used for pressure, volume, mass, and temperature. For fairly close
approximations, a modified formula can be used that is written as

PV=ZnRT
where Z is known as the compressibility factor and can be obtained from a chart
such as shown in Fig. 5.2, a generalized compressibility chart. 23 To use this chart,
it is necessary to use reduced pressures and temperatures to evaluate Z. The reduced
temperature, Tn is equal to the actual temperature (in units ofK or OR) divided by
the critical temperature of the gas (in the same units). Similarly, the reduced
pressure, P n is the actual (absolute) pressure divided by the critical pressure. Table
5.3 gives values of the critical constants for some of the more common cryogens.
To calculate a final pressure, it is frequently necessary to use an iterative procedure.
Unfortunately, with respect to limiting the rate of pressure rise in a Dewar,
thermal gradients are frequently encountered within cryogenic storage systems.
Figure 5.3 shows a horizontal cross section through either a spherical Dewar or a
horizontal, cylindrical Dewar. As shown, the heat will penetrate the insulation space
all around the circumference ofthe Dewar. The assumption of thermal equilibrium
implies that all of the liquid cryogen will be equally heated by the heat entering the
Dewar. When a Dewar has been venting against a constant discharge pressure for
a long time, the temperature will be fairly evenly distributed in the interior, except
for a small temperature gradient caused by the hydrostatic head in the fluid.

Table 5.3. Critical Constants of Some Common Cryogens

Cryogen Critical temperature (K) Critical pressure [MPa (psi)]


Helium 5.3 0.23 (33.2)
Nonna1 hydrogen 33.2 1.31 (190.0)
Parahydrogen 33.0 1.29 (187.5)
Neon 44.5 2.73 (395)
Nitrogen 126.2 3.39 (492)
Oxygen 154.6 5.04 (731)
Argon 150.9 4.90 (711)
58 Chapter 5

_______ warrn_ Layer~ ___________ _


Heat to
Surface 1\
I \
\

Fig. 5.3. Distribution of heat input into a cryogenic Dewar. Except for the heat entering the area at the
bottom of the Dewar, the heat that enters the storage volwne forms a warmer layer that can slide up the
inner wall and accumulate on the liquid surface.

However, when the vent is closed, then the temperature can start to stratify. Under
this circumstance, the heat that enters the sides of the Dewar first reaches the outer
layer of liquid, which, because of its slightly lower density, can slide up the inner
wall and collect on the liquid surface. The result ofthis process is that a warm layer
will slowly accumulate on the liquid surface and gradually grow in thickness. If the
Dewar is then allowed to vent at a higher temperature (and also a higher pressure),
given a long enough time, the warmer liquid layer will grow to fill the Dewar, and
thermal equilibrium will once more be approached. However, the pressure in the
Dewar will always be determined by the temperature ofthe liquid surface (its vapor
pressure). When the Dewar is closed off so that venting cannot occur, the heat
energy input into the Dewar is not equally distributed through all the liquid, and
the surface will have more than its share of the energy. Thus, the Dewar will
self-pressurize more quickly than would be the case were thermal equilibrium to
exist.
An example of this phenomenon was seen in the early 1950s during the
transport of liquid hydrogen in a 6_m3 (6000 L) trailer-mounted transport Dewar
from Boulder, Colorado, to Los Alamos, New Mexico. 4 This 644-km (400 mile)
trip involves a number of elevation changes, from an elevation of about 1630 m
(5350 ft) above sea level at Boulder to 1430 m (4700 ft) at Pueblo, Colorado, to
almost 3049 m (10,000 ft) over La Veta Pass to 1677 m (5500 ft) at Espanola, New
Mexico, to 2240 m (7350 ft) at the Los Alamos National Laboratory. During this
trip there was a concern that on one or more of the descents, the external atmos-
Buildup of Pressure 59

pheric pressure could rise fast enough that air could enter the Dewar and condense
to a solid with essentially zero vapor pressure, and the resulting mixture, which
could be dangerous, would give no evidence of its presence. Calculations made
with the use of the known heat leak into the Dewar showed that the Dewar could
be closed off for the 10-hour trip with a rise in pressure of only about 0.07 MPa
(10 psi). The 0.7-MPa (100 psi) pressure rating of the Dewar made it acceptable to
close off the Dewar at the start of the trip and then vent it back down to local
atmospheric pressure upon its arrival. This procedure was followed, and on the first
trip, after about two hours, the driver stopped for lunch. At that time the pressure
rise was seen to be about 0.014 MPa (2 psi), which was about what was expected.
During the time that the trailer was parked (approximately an hour), the pressure
rose about 0.07 MPa (10 psi). This was a cause for concern. However, the technical
courier realized that this inordinate pressure rise was probably caused by thermal
stratification within the Dewar and told the driver to start driving the truck. As soon
as the trailer was under way, the pressure then decreased to almost the same reading
that it had before the pause in the journey. The vibration of the stored fluid while
in motion was sufficient to thoroughly mix the fluid and bring it back to thermal
equilibrium. The remainder of the trip was uneventful.
Another example ofthe effects of thermal stratification was demonstrated with
an experiment performed at the Nuclear Rocket Development Station in Nevada
during the Rover Program (Nuclear Rocket Program). 5 In between two of the earlier
reactor tests, the vent systems were closed on two identica1200-m3 (50,000 gallon)
liquid-hydrogen storage Dewars. The boil-off had been measured previously and
shown to be the same for each of the Dewars. The results of this test are shown in
Fig. 5.4, from which it can be seen that the rate of pressure rise in one Dewar was
approximately three times that in the other. In Fig 5.4 the line with the lowest slope
is from a computation of the rate of pressure rise to be expected if thermal
equilibrium were present at all times within the Dewar. The line with the highest
pressure rise rate results from a calculation that assumed that all of the heat input
energy is deposited in a very thin layer at the top ofthe liquid (essentially all energy
goes into the ullage gas). Actually, neither of these limits could be attained, and an
intermediate behavior was expected. However, the variation by a factor of 3
between the two actual rates was unexpected. As required by the system design, the
two Dewars were connected to a common discharge line with one shutoff valve in
each Dewar discharge line and another shutoff valve in the common line down-
stream. This arrangement is discussed later in Chapter 7 and is shown in Fig. 7.2.
The volume contained between the three shutoff valves had been maintained filled
with helium gas at a pressure slightly higher than the maximum storage pressure in
the Dewars. The purpose of this procedure was to prevent leakage of liquid
hydrogen out ofthe storage Dewar in the event of a leak in the Dewar shutoff valve.
Examination, by gas analysis, of the gas in the ullage spaces of the Dewars showed
that helium gas had leaked into the Dewar that had the lower pressure rise rate. The
60 ChapterS

3~,-----------.-----------.----------,.---------~

Curve A, Calculated
(Energy Absorption by Ullage Only)

300+-----------~--~~--~----------+_--------~

Ii'
~2~1------------H~--------~-----------+--~------~
!

a.
~
~~ 200 1_-------I---~--------____"......- Curve B, Observed
from Dewar A
<0(

1~+-~--~L---+_------~~~=-------

Curve D, Calculated
(Uniform Energy Absorption, Uquid Only)

100~~~--~~~~--~T-~_+~--r-~~-+--~T-~~~
o 10 20 30 40
Time From Start (h)

Fig. 5.4. Pressure buildup from self-pressurization in two identical liquid-hydrogen storage Dewars. 5

helium leaking in was sufficient to stir the liquid hydrogen, keeping it closer to
thermal equilibrium throughout its volume. Thus, the helium gas leaking into this
Dewar resulted in a lower pressure rise rate than would have been the case if no
helium had been introduced.
Another experiment was performed on one of the above liquid-hydrogen
storage Dewars. 5 The Dewar was equipped with a vertical instrumentation rake
with a number of temperature-measuring elements to measure temperature as a
function ofliquid-hydrogen depth in the Dewar. Figure 5.5 shows the temperature
profile in the Dewar initially and then 38 h after the Dewar vents were closed. Here
it can be seen that, within the limits of sensitivity of the thermometers as shown on
the graph, the temperature of the bulk of the fluid did not change, and only on the
surface was there a noticeable increase in temperature. Also, it can be seen that the
E.
=
s:
C
't:S
So
."
til
~
c
til

20 40 60 80 100
Temperature (I<)
CI\
Fig. 5.5. Temperature profiles during self-pressurization in a liquid-hydrogen storage Dewar.5 -
62 Chapter 5

pressure rise over the 38-h period was about 0.l4 MPa (20 psi), and the surface
temperature during this time increased from 21.2 K to 24.2 K.
The data from Figs. 5.4 and 5.5 show that the pressure rise in a well-insulated,
large storage Dewar can be slow. However, it must be remembered that for such
Dewars the geometric configuration is favorable in terms of having the best possible
surface-to-volume ratio (spherical) and the insulation is good (I-m thickness of
evacuated perlite powder). Thus, the relative heat input is also low. Smaller systems
will experience faster pressure rises, and, of course, if the insulation should be
compromised (such as through a loss of insulating vacuum), the pressure can rise
much faster.
Another factor that must be borne in mind is that the lower the boiling
temperature of a cryogen, the greater is the temperature difference from ambient
temperature, or the driving force for heat introduction, and thus the greater is the
potential for a more rapid pressure rise. Table 1.1 lists the heats of vaporization on
a mass basis (kJ/kg) for common cryogens. For the consideration of pressure rise
in a vessel, it is also instructive to consider the heat of vaporization on a volume
basis (kJ/m 3 ). From the data in Table 1.1, one can calculate the heat of vaporization
per unit volume, showing it to decrease with decreasing normal boiling tempera-
ture. Thus, the same quantity of heat can evaporate more liquid as one progresses
to lower-boiling cryogens. At the same time, the temperature difference between
ambient temperature and cryogen storage temperature (the driving force for forcing
heat into the cryogenic system) is increasing. The vaporization index, VI, or
temperature difference divided by the volume heat of vaporization, is listed in the
last column in Table 1.1 and is a measure of the difficulty of storing and handling
a given cryogen as well as of its tendency to increase in pressure if confined.
The importance of maintaining the proper degree of vacuum in the insulation
space of either evacuated powder or evacuated multilayer insulation systems cannot
be overemphasized. Several publications in the cryogenic literature have given
correlations of the increase in effective thermal conductivity as the vacuum in an
evacuated thermal insulation system deteriorates. Over the range from the preferred
vacuum for evacuated perlite powder (about 1.3 Pa or 10-2 Torr) to 1 atm of air, the
effective thermal conductivity can be seen to increase by a factor of about 30. 6 For
multilayer thermal insulation the increase of pressure in the insulation space from
a maximum residual pressure of about 0.013 Pa (I 0--4 Torr) to 1 atm can cause a
corresponding increase of effective thermal conductivity of a factor of about 600. 6
Of course, the total heat input to the cryogen storage area is the sum of the heat
leaks through the insulation as well as from the support system and interconnecting
piping and instrumentation wires. For this reason the heat input into the Dewar will
not rise quite as rapidly as the above numbers might indicate. To estimate the
increase in the total rate of heat input would require a detailed knowledge of the
Dewar design. However, the effect of the increased thermal conductivity of the
Buildup of Pressure 63

thermal insulation will be by far the most important factor in causing either a much
higher evaporation rate or a much higher rate of pressure increase.

5.2. OVERPRESSURE PROTECTION

Because of the potential for increase in pressure, all cryogenic systems must
be protected against the trapping of cryogenic liquids, or even cold gases. Systems
should be equipped with duplicate, redundant venting systems. Often such an
arrangement consists of a relief valve in parallel with a rupture disk. In the design
of pressure relief systems, it should be remembered that the relief devices should
be sufficiently thermally spaced from the cold volumes so that they remain at
ambient temperature. The cooling of these devices can change the strength of the
bursting disk metal or the response to rising pressure of the relief valve and therefore
change the pressure at which they will relieve. Reliefvalves should be periodically
tested to see that they still operate as expected. Also, rupture disks should be
replaced periodically to prevent their becoming work-hardened by pressure vari-
ations within the volume being protected. It must be remembered that relief valves
may not reseat until warmed to room temperature.
Relief systems must be sized to be sufficiently large to accommodate the
maximum flow rate of either gas or liquid that could occur. The flow through the
relief valve or rupture disk must be adequate to be able to prevent the system
pressure from rising above its maximum allowable working pressure (MAWP). The
maximum boil-off rate of the stored cryogen should be calculated for the specific
cryogenic system being protected, and the relief valve sized accordingly.
Figure 5.6 shows a typical arrangement for the vent system for a large storage
Dewar. In this case two vent paths have been chosen, one for normal boil-offventing
and a second path for more rapid, operational venting when necessary. A separate
vent path should be provided for relief valve and rupture disk operation. A separate
relief path is also necessary for the evacuated insulation space. For cryogens that
boil at the higher end of the cryogenic range, the pressure relief on the evacuated
insulation space is necessary in case fluid leaks into it from the inner container. As
mentioned previously, liquid-hydrogen, liquid-helium, or liquid-neon storage De-
wars must also be protected against a leak from the external atmosphere. 1
In order to eliminate the possibility of air intrusion into the interior of a
cryogenic Dewar, it is usually a good idea to maintain the fluid storage space at a
pressure slightly above that of the local atmosphere. Even if the fluid container in
a cryogenic Dewar is to be operated at essentially atmospheric pressure, it still is
considered to be a pressure vessel because it is surrounded by a vacuum jacket.
Therefore, cryogen storage vessels must be designed and tested according the
ASME Pressure Vessel Code, Section VIII, for unfired pressure vessels. There may
be a problem with hydrostatic testing of a storage vessel that is designed for
64 ChapterS

Fig. 5.6. Schematic of typical vent


system for a large liquid-hydrogen
storage Dewar l : (I) Dewar pressuriza-
tion valve; (2) fast vent valve; (3) nor-
mal boil-off control valve; (4) safety
relief valve; (5) rupture disk; (6) gas
pressurization/vent ring (holes on top
side only help preserve thermal strati-
fication and reduce liquid entrainment
in vent gas); (7) liquid discharge
valve; (8) pressure relief valve for an-
nulus.

liquid-hydrogen or liquid-helium service because of the very low density of these


fluids (see Table 1.1). Ifpossible, the vessel should be pressure-tested at the normal
working temperature. The highest pressure that is permissible for the vessel to
experience is the MAWP. Normal working pressure will be less than the MAWP.
For cryogenic storage vessels with two relief devices, the pressure relief valve
is usually set to relieve at 10% above the normal working pressure, and the rupture
disk is set to relieve at 20% above the normal working pressure (or at the MAWP).
It must be remembered that these pressures must be based on the vessel gauge
pressure (referred to the external atmosphere) plus the pressure of the local
atmosphere. The required size of the safety valve is determined by the maximum
amount of vapor evolution that could occur (such as ifthere would be a complete
loss of the vacuum in the insulation space). According to the ASME Code, the flow
area, A, of the relief device can be determined by

A = m/RT/g)1)J12/KCPmax

where A is the flow area of the valve (m2), mj is the maximum mass flow rate from the
vessel (kgls),R is the universal gas constant [8314NmJ(kmolK) (1545 ftlbfflbmol OR)],
T is the absolute temperature of the gas at the inlet to the valve (K), gc is the unit
conversion factor in Newton's second law [1 kgmJ(Ns2) (SI units)], M is the
molecular weight of the gas (kg/kmol), K is the discharge coefficient (measured),
C is the expansion factor, and P max is the pressure at the inlet to the relief valve (Pa
= N/m2). The expansion factor, C, is determined by
C = {y[2/(y + 1)](y + J)/(y - I)} 112
Buildup of Pressure 65

where y is the ratio ofthe specific heats of the gas (Cpl Cv ),6,7 and Pmax is determined
by
P max = (Ll) [working gauge pressure (not MAWP)] + atmospheric pressure

Under some circumstances, the above assumption of a maximum vent rate


corresponding to a loss of vacuum in the insulation space could result in an
inadequate relief valve size. This could be the case if the vessel is overfilled, or if
the venting is so rapid that liquid could be entrained with the venting gas, or if the
vessel could be upset so that the opening leading to the relief valve is submerged
in the liquid. In this case the venting rate must be adequate to accommodate the rate
of volume evolution within the vapor space of the Dewar. Thus, if liquid is being
vented, the venting stream will have a higher density, but a considerably larger mass
flow will be required. 8
The discharge of all vent systems must be located so that cold fluids cannot
impinge upon personnel or upon equipment that could be damaged by the cold fluid
being vented. Also, there should be no cold surfaces in any location where they
could be inadvertently touched by personnel. Another important consideration is
that when the vented fluid is sufficiently cold for air to condense on the outside of
the vent pipe, the condensate must not be allowed to fall on sensitive material or
equipment. Obvious examples of materials that must not be subjected to a stream
of condensed air (which can be enriched in oxygen to about 50%) are asphalt, tar,
or any other combustible. Electronic equipment or equipment with movable or
rotating parts can also be deleteriously affected. Some metals are also affected if
they are not suitable for low-temperature service (see Chapter 3). To prevent any
of these hazards, it might be necessary to apply thermal insulation to some parts of
the vent system.
The vent system should be sufficiently instrumented to enable the operators
to ensure that all of the components are in operating condition and that venting is
actually occurring when venting is desired. The instrumentation can include such
sensors as pressure transducers, thermometers, flow meters, liquid-level detectors,
and perhaps sound monitors (microphones).

5.3. THERMAL EXPANSION AS A SOURCE OF OVERPRESSURE

In the filling of cryogenic systems, the relatively large thermal expansion of


the cryogen as it warms must be taken into account. Table 5.4 presents thermal
expansion coefficients for some of the more common cryogens. From Table 5.4 it
can be seen that every one ofthe listed cryogens has a thermal expansion coefficient
(change in volume divided by initial volume per kelvin) at least 10 times as great
as that of water. Also, as the progression is made to cryogens with lower boiling
temperatures, there is a corresponding increase in the thermal expansion coefficient.
66 ChapterS

Table S.4. Thermal Expansion Coefficients


[(ltv) (dV I dT)p) of Some CryogensQ

Thermal expansion
Liquid coefficient (K- 1)
Waterb 0.0007
Oxygen 0.0044
Argon 0.0044
Nitrogen 0.0057
Neon 0.0144
Hydrogen 0.0164
Helium 0.210

a At normal boiling point.


b Included for comparison purposes.

Consequently, care must be taken to avoid overfilling cryogenic liquid storage


systems.
Typically, large storage Dewars are designed with ullage spaces of about 10%
so that the Dewar cannot be completely filled with liquid. If the vent system is
closed off and the pressure in the Dewar is allowed to rise, and with it the
temperature of the stored liquid, a considerable increase in liquid volume will occur.
The increase in pressure can condense some of the gas in the ullage and make space
for the expanding liquid. Ifthe liquid expands sufficiently to fill the entire accessible
volume, the vessel is said to be "liquid full." The Dewar should not be allowed to
be liquid full, because at this point there will be a much more rapid rise in pressure.
Also, if this were to happen and then the relief system were to function, liquid would
be ejected from the Dewar, and the vent system might not be able to handle the
vented fluid without undue pressure rise.

5.4. PRESSURE OSCILLATIONS AS A SOURCE OF OVERPRESSURE

Pressure oscillations frequently occur in cryogenic systems and could consti-


tute a hazard under some circumstances. There are a number of mechanisms to
incite these oscillations, and their frequencies and amplitudes can cover a fairly
large range.

5.4.1. Flow Oscillations


The flow of cryogens is frequently accompanied by the transfer of heat, either
as a transient process in the cooling of cryogenic pipelines to operating temperature
or in continuous operation of a heat exchanger. If the pressure is below the critical
Buildup of Pressure 67

pressure, usually two-phase flow will be encountered, and the rapid and large
change in volume between the liquid and gas can give rise to significant pressure
and flow oscillations. Temporary flow reversals can be encountered. Above the
critical pressure, these oscillations can still occur if the operation is near the
transposed critical line, where, even without vaporization, large volume changes
can occur over a small temperature range.
There are several mechanisms to produce oscillations, and the frequency of
these oscillations can vary from about 0.05 Hz to 10,000 Hz. In some cases the
pressure amplitude can be of the order of one-third of the system static pressure. 9
One mode of pressure oscillations was investigated by Bronson et al., 10 who
showed that the frequency of these oscillations occurring during the cool-down of
a long cryogenic transfer line could be analyzed by considering a spring-mass
system, a so-called Helmholtz oscillation. The gas in the warm, downstream portion
of the line was analogous to the spring, and the liquid in the upstream portion of
the line, where cooling was almost complete, could function as the mass suspended
on the spring. Experimental measurements of oscillations with a frequency of about
2 Hz in a I5-m-Iong (50-ft-Iong) transfer line being cooled with liquid hydrogen
showed good agreement with the theoretically derived relationship:

where fis frequency (Hz), y = Cp/Cv (ratio of specific heats), P is pressure (Pa),
LL is the length ofline already cooled and filled with liquid (m), Lg is the length of
line yet to be cooled and filled with gas (m), and p is the density of the liquid,
(kg/m3).
Thurston et al. II studied the conditions that produced Helmholtz oscillations
as well as acoustically driven oscillations, and Rogers 12 developed the following
empirical relationship with which they were able to predict the onset of these
oscillations:

Nboi = O.005/Nsv

where Nboi (the boiling number for incipient oscillations to persist) is defined as
Nboi = q/GMlv = (heat flux)/[(mass flux)(heat of vaporization)], with units of
(J/sm2)/[(kglsm2)(J/kg)] (thus Nboi is dimensionless), and Nsv is the dimensionless
specific volume number, given by(VG - VL)/VL , where VG is the volume of gas and
VL is the volume of liquid. If the actual boiling number, Nbo , is less than Nboi ,
oscillations will not persist, but if Nbo is greater than Nboj ' oscillations will persist.
Also, with the use of an amplitude number:
68 ChapterS

where p is the amplitude of the pressure variations,fis the frequency of the pressure
oscillations, D j is the pipe inside diameter, and G and llHvare as defined above,
they were able to correlate pressure amplitudes to within 40% by

Nam = O.Oll(Nbo - Nbof 66

Note that the boiling number, the specific volume number, and the amplitude
number are all dimensionless ratios and require the use of consistent units in their
evaluation. II

5.4.2. Thermal Acoustic Oscillations


Thermal acoustic oscillations (TAO) frequently occur whenever a long tube
connects a region at cryogenic temperature with an ambient-temperature region
(300 K). Such tubes are usually present in cryogenic storage systems for instrumen-
tation ports or for fluid flow. These oscillations, which are particularly pronounced
if the cryogen being stored is either liquid hydrogen or liquid helium, can occur
without any net flow of fluid or any intended transfer of heat.
Along its length, the tube must sustain the temperature gradient between 300 K
and the temperature ofthe cryogen. Any perturbation that can cause a slight advance
of the liquid within the tube will warm the fluid and consequently give rise to some
local expansion, causing the liquid to retreat, which in tum allows the gas to flow
back into the somewhat cooled line. This in tum lowers the gas pressure and induces
the inflow of the liquid again. The repetition of this process causes a pressure
oscillation that does not damp and that can pump thermal energy into the stored
liquid. In some cases this process can greatly multiply the heat input to the storage
area. This additional energy input, in addition to the pressure surges, is undesirable.
The pressure surges can sometimes render the measurement of pressure impossible.

Guand Timmerhaus l3 have studied the conditions under which TAO can occur
in liquid hydrogen and liquid helium. One ofthe determining parameters is the ratio
of the temperature at the warm end of the tube to that at the cold end. The latter
temperature is not necessarily as cold as that ofthe liquid because ofthe possibility
of a thermal gradient in the ullage space above the liquid phase as well as from the
heat being conducted down the length of the tube along the thermal gradient that it
supports. The other parameters that determine whether an existing oscillation will
persist or die out are the temperature gradient along the tube, the diameter of the
tube, and the ratio of the length of the tube that approximates the warm temperature
to the length that approximates the cold temperature. These lengths would be easier
to determine ifthere were a discontinuous temperature gradient with all the change
in temperature taking place at a finite point along the tube. Although the gradient
may be steep at a point in the tube, it is not a step function. The shape of the
temperature gradient is also a factor in influencing the existence and frequency of
Buildup of Pressure 69

TAO. The closer the temperature gradient is to being linear, the less likely it is that
the oscillations will occur, but the higher is their frequency. Also, the closer to equal
the cold and warm lengths of the tube, the more likely it is that oscillations can
occur. For liquid helium, Gu and Timmerhaus found that tube diameters of about
1-2 mm are the most likely to allow the persistence of the oscillations. If the
diameter is smaller, the viscous drag will exert greater influence for damping, and
if the tube diameter is larger, the fluid inertia can exert a greater damping force. For
liquid helium they observed pressure oscillations with an amplitude in the vicinity
of 20 kPa (150 Torr).13 The figures in the paper by Gu and Timmerhaus allow an
estimate to be made of the conditions under which TAO will exist. For other fluids,
additional calculations must be made.

5.5. ROLLOVER

Rollover is a phenomenon that is usually associated with the storage of


liquefied natural gas (LNG). However, a similar occurrence takes place in lakes
before freezing takes place. In the latter case, the surface water becomes more dense
and sinks to the bottom, allowing warmer water to come to the surface, and thus
no freezing takes place until the entire body of water is cooled to approximately
4 cC. A similar phenomenon has occurred in the Dead Sea, where surface
evaporation ofthe water has resulted in a denser layer on the surface that eventually
sank:, allowing the subsurface water to rise.
Rollover, in the case of natural gas, can be of concern because of increased
rate of vapor evolution. LNG is not a single-component fluid but rather has a
number of constituents, each with a different vapor pressure and a different density
at any given temperature. When loading LNG into a tank: with some residual liquid,
referred to as "heel," the two fluids may have different densities, and they may
stratify. This can happen if a fluid with a larger percentage of higher-molecular-
weight constituents is loaded by a bottom fill technique. Because LNG is a
cryogenic liquid, it is always subjected to the input of heat from the environment.
The heat and mass transfer within the tank are slow processes and are further
impeded by the difference in densities. Although heat is entering the tank both
through the bottom and the sides, the top layer can lose heat by evaporation,
preferentially of its lighter constituents, whereas the bottom layer can lose heat only
by conduction to the top layer. Consequently, the bottom layer tends to warm up
and its density tends to decrease while the top layer loses its lighter constituents
and becomes heavier. When the layers approach the same density, rapid mixing can
occur. As the lower fluid, which is now warmer and has higher vapor pressure,
approaches the surface, it is also suddenly relieved of hydrostatic pressure and can
boil vigorously. 14 The large increase in boil-off can be a hazard, because the vapors
resulting from the evaporation of LNG are combustible and can be explosive if
70 ChapterS

ignited under confined conditions. However, the hazard will be even greater if the
relief valves have not been sized to handle the greater than normal flow rate of the
boil-off vapors. Ifthey do not accommodate the increased flow rate at the maximum
pressure that the tank can stand, the pressure in the tank can rise sufficiently to
damage or even rupture the tank. The phenomenon of rollover has been known to
occur on a number of occasions. To the knowledge of the authors, no incident of
tank rupture has been caused by this phenomenon. Pressure relief valves have been
activated, but ignition of the evolved vapor has not occurred. IS Rollover presents
another mechanism by which there could be an abnormal pressure rise within a
cryogenic container; however, preventive measures that can be taken include
mixing of the stored fluid and decreasing the nitrogen content of the fluid.

5.6. QUENCHING OF SUPERCONDUCTING MAGNETS

The quenching of a superconducting magnet can cause a rapid conversion of


stored electrical energy to thermal energy. The energy stored in the magnet is equal
to (Li)12, where L is the inductance of the coil and I is the current. If the
superconductor in the winding of the magnet develops a normal, or nonsupercon-
ducting, spot, local ohmic (or iR) heating occurs (R is the electrical resistance). If
this heat evolution rate is greater than the heat removal rate caused by heat transfer
to the coolant and thermal conduction along the wire, the normal spot will grow
until the entire superconductor in the magnet is warmed sufficiently to enter the
nonsuperconducting state. The electrical resistance thus manifested will cause the
current to decay, and the magnet is said to be "quenched."
The quenching process converts the stored electrical energy into thermal
energy and causes rapid heating in the magnet. The distribution of the thermal
energy, and consequently the local temperature, depends upon the rate ofpropaga-
tion of the normal zone and the degree of stabilization provided by the design of
the magnet. Local temperatures can become sufficiently high to melt the conductors
and destroy the magnet. 16
The normal zone will grow at a rate determined by the ohmic heating rate and
the rate at which the heat is removed. In cooling the wire, the coolant fluid will be
heated, giving rise to an increase in the cooling system pressure. Thus, the magnet
can be physically damaged either by excess temperature or by excess pressure. The
excess pressure can also present an overpressure hazard to the surroundings.
Preventing the occurrences of quenches and ensuring that the magnet can
survive them if they do occur are of primary importance in the design of the magnet.
Predicting the rate of heating of the coolant fluid, helium in most cases to date, is
a difficult problem. The solution must consider three-dimensional heat transfer and
variations in heat capacities and electrical resistivities by several orders of magni-
Buildup of Pressure 71

tude. The degree of stabilization will determine the rate of normal-zone propagation
and also provide thermal capacity to limit the temperature rise.
With magnets cooled by immersion, pool boiling will occur. In the case of
magnets cooled by a forced flow of supercritical helium, the flow dynamics and
the convective heat-transfer coefficient will be strongly affected by the expanding
pressure pulse generated in the normal zone. The heating of the coolant fluid will
cause a corresponding pressure increase. In the case of large magnets, very high
pressures can be reached. For a 20-pancake coil with 12 turns/pancake, the total
coolant path length amounted to 446 m. If the full length of one pancake coil were
to quench, preliminary calculations indicate that a pressure in the vicinity of 43 MPa
could be reached even if the coil were vented. (Pressures on the order of 130 MPa
have been predicted in the case of an unvented pancake coil. 17) Thus, pressure relief
is required, and the pressure relief system must be sufficiently large to accommo-
date the venting of coolant needed to maintain a safe pressure within the magnet
enclosure.
The required vent rate will depend upon the magnet design, the rate of growth
of the normal zone,16 and consequent ohmic heating of the wire, and the rate at
which the heat transfer will allow this energy to enter the coolant.
The development of magnets utilizing high-temperature superconductors may
ease this problem somewhat because of the large increase in heat capacity of many
materials as the temperature is raised to the vicinity of75 K.

REFERENCES
1. Edeskuty, F. J. (1979). Safety, in Hydrogen: Its Technology and Implications (K. E. Cox and K.
D. Williamson, Jr., eds.), Vol. IV, Chap. 5, CRC Press, Boca Raton, Florida.
2. Van Wy1en, G. J., and Sonntag, R. E. (1987). Fundamentals o/Classical Thermodynamics, 3rd
Ed., John Wiley & Sons, New York.
3. Dodge, B. F. (1944). Chemical Engineering Thermodynamics, McGraw-Hill, New York.
4. Laquer, H. L. personal communication.
5. Edeskuty, F. J., and Williamson, K. D., Jr. (1977). Liquid hydrogen storage and transmission, in
Hydrogen: Its Technology and Implications (K. E. Cox and K. D. Williamson, Jr., eds.), Vol. II,
Chap. 3, CRC Press, Boca Raton, Florida.
6. Barron, R. F. (1985). Cryogenic Systems, 2nd Ed., Oxford University Press, New York.
7. Timmerhaus, K. D., and Flynn, T. M. (1989). Cryogenic Process Engineering, Plenum Press, New
York.
8. Sallet, D. W. (1978). On the sizing of pressure relief valves for pressure vessels which are used in
the transport of liquefied gases, Paper 78-WA/HY-39, presented at the ASME Winter Annual
Meeting, San Francisco, California, December 10-15, 1978, American Society of Mechanical
Engineers, New York.
9. Smith, R. V. (1971). Fluid dynamics, in Cryogenic Fundamentals (G. G. Haselden, ed.), Chap. 5,
Academic Press, London.
10. Bronson, J. C., Edeskuty, F. J., Fretwell, J. H., Hammel, E. F., Keller, W. E., Meier, K. L., Schuch,
A. F., and Willis, W. L. (1962). Problems in cool-down of cryogenic systems, in Advances in
Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 7, pp. 198-205, Plenum Press, New York.
72 ChapterS

II. Thurston, R. S., Rogers, J. D., and Skoglund, V. J. (1967). Pressure oscillations induced by forced
convection heating of dense hydrogen, in Advances in Cryogenic Engineering (K. D. Tirnmerhaus,
ed.), Vol. 12, pp. 438-451, Plenum Press, New York.
12. Rogers, 1. D. (1968). Oscillations in flowing and heated subcritical hydrogen, in Advances in
Cryogenic Engineering (K. D. Tirnmerhaus, ed.), Vol. 13, pp. 223--231, Plenum Press, New York.
13. Gu, Y., and Tirnmerhaus, K. D. (1994). Experimental verification of stability characteristics for
thermal acoustic oscillations in a liquid helium system, in Advances in Cryogenic Engineering (P.
Kittel, ed.), Vol. 39B, pp. 1733--1740, Plenum Press, New York.
14. Johnson, P. C. (1983). Liquefied natural gas, in Liquid Cryogens (K. D. Williamson, Jr., and F. J.
Edeskuty, eds.), Vol. II, Chap. 3, CRC Press, Boca Raton, Florida.
15. Sarsten, 1. A. (1972). LNG stratification and rollover, Pipeline Gas 1. 199(9), 37.
16. Wilson, M. N. (1983). Superconducting Magnets, Clarendon Press, Oxford.
17. Slack, D. S. (1989). Analysis of quench-vent pressures for present design ofITER TF Coils, Paper
presented at the 13th Symposium on Fusion Engineering, Knoxville, Tennessee, October 2-6,
1989.
Chapter 6

Condensation

All cryogens can present the hazard of unwanted condensation of substances that
boil at higher temperatures. Table 6.1 shows the estimated vapor pressures of some
of the substances that, ifpresent, can be condensed, usually to a solid, at cryogenic
temperatures. I From the magnitude of these vapor pressures it can be seen that, in
some cases, even undetectable amounts of substances can be condensed, although
probably only negligible quantities of solids could accumulate at such low concen-
trations. Table 6.1 indicates that any cryogen can almost totally condense water
vapor and carbon dioxide. Air can be condensed to a liquid at liquid-nitrogen
temperatures (possibly resulting in a condensate enriched in oxygen; see Section
6.1.2.). Argon, nitrogen, and oxygen are condensed to solids at the temperatures of
liquid neon, liquid hydrogen, or liquid helium. Finally, all substances, other than
helium, are solids at the temperature of liquid helium.
The ability ofliquid nitrogen to condense higher-boiling constituents affords
an inexpensive and very effective means to remove water vapor and carbon dioxide
to the extent that they exhibit essentially zero vapor pressure at 77 K. Frequent use

Table 6.1. Estimated Vapor Pressure of Some Gases at Selected Temperatures Q

Estimated vapor pressure (Torr) at:


Triple pointb
Vapor T=4K T=20K T=77K T= 150 K (K)
Water c c c _10-7 273
c c -IO-s
Carbon dioxide -10 217
Argon c _10- 13 -160 d
84
Oxygen c _10- 13 -150 d
54
Nitrogen
c _10- 11 -730 d
63
c d d
Neon -30 25
Hydrogen _10-7 -760 d d
14

a Values are estimates, useful for comparison purposes.


b Only solid and vapor can be at equilibrium below this temperature (no liquid).
C Negligible, less than 10-13 Torr.

d Greater than one atmosphere (760 Torr).

73
74 Chapter 6

is made of this condensation process in cold traps to quantitatively remove water


vapor, carbon dioxide, and other higher-boiling constituents from vacuum systems
and other places where these constituents are not wanted. The effectiveness of this
means of vapor removal is also demonstrated by the performance of the cryopump,
which uses cryogenic temperatures (down to 4 K) to reach very high vacuum in
even very large systems.

6.1. HAZARDS ARISING FROM UNWANTED CONDENSATION

There are several ways in which the condensation of an unwanted substance


can present a hazard in work with cryogenic systems. These hazards can be either
mechanical or chemical in nature. If the condensation is internal to a cryogenic
system, a mechanical hazard could result from plugging of pressure relief ports or
erosion of valve seats within the system. A mechanical hazard can also arise by cold
embrittlement or by stresses caused by unaccommodated thermal contraction that
would result from the dripping of condensed air on other equipment. A chemical
hazard could result by the flow of oxygen-rich condensed air onto combustible
materials.

6.1.1. Condensation and Freezing of Inert Substances


Even though no chemical reaction such as combustion is involved, the con-
densation of a solid within an otherwise fluid system can cause damage that can
lead to a hazardous situation?,3 If entrained in a flowing stream, the solid particles
can erode valve seats or packing and gasket material. The resulting leakage can
present a hazard.
Under some circumstances, fairly massive amounts of condensed solids can
accumulate. Unfortunately, it is seldom possible to observe visually the interior of
a cryogenic system, and the condensed solids with undetectable vapor pressure can
be present in large quantities without giving any evidence of their presence. If a
sufficiently large quantity could accumulate to plug a pipe or tube opening, and if
this were to occur in the entrance to a relief valve, or in some cases even an
instrumentation port, a serious hazard would result. Another consequence might be
that the ability to purge the system could be compromised.
In the case of a leak of air into the vacuum insulation space surrounding a
vessel containing liquid neon, liquid hydrogen, or liquid helium, the air will
condense on the inner surface of the vacuum space and give no evidence of its
presence. If the vessel is maintained in its cold state for a sufficiently long time,
then, upon the eventual warming of the vessel, there could be enough solid air
collected in the vacuum space to exert a positive pressure in the space where
normally a vacuum is expected to be present. This positive pressure could be large
enough either to crush the inner vessel or perhaps even to burst the vacuum jacket.4
Condensation 75

6.1.2. Condensation of Substances Forming Combustible Mixtures


Air or oxygen condensing in liquid hydrogen results in a potentially combus-
tible (or explosive) mixture. The condensate of air can be enriched in oxygen above
the corresponding composition of the vapor being condensed? Figure 6.1 shows
that as long as normal air with an oxygen concentration of approximately 21%
oxygen is in contact with the cold surface (below about 82 K), the condensate will
be about 50% oxygen. 5 This increased oxygen content makes the condensate more
hazardous than liquid air (21 % oxygen). The subsequent evaporation of the con-
densate can result in even further oxygen enrichment.
In the presence of oxygen, or oxygen-enriched atmospheres, some substances
that might normally be noncombustible can bum, and substances that bum in
normal air will bum much more vigorously or can even react explosively (see

Atmospheric Composition Vapor


I

nK Liquid

Fig. 6.1. Oxygen/nitrogen phase equilibrium diagram at 1 atm pressure. 5 Line A-B connects the
composition of condensing air to that of the condensate.
76 Chapter 6

Chapter 9). If the atmospheric air is condensed, the condensate, which is enriched
in oxygen, as mentioned above, can cause an explosive hazard if it is allowed to
fall upon a combustible surface such as an asphalt driveway. It is for this reason
that at liquid-hydrogen-unloading sites, the area under the storage Dewar, the
connecting piping, and the delivery trailer are always paved with concrete.
In the case of oxygen or air being condensed in liquid hydrogen, the exact
ignition mechanism may not be obvious, but combustion could be started by such
an occurrence as the rupture of a solid oxygen crystal by impact or by closing a
valve on the crystal. Also, in the case of fluid flow, the presence of solid crystals
can promote the accumulation of an electric charge on the particle. Therefore,
another possibility for ignition would be a spark caused by a buildup of electric
charge (see Chapter 12). In any case, the disposal of the liquid-solid mixture could
also present a hazard.

6.1.3. External Condensation on Cold Surfaces


The condensation of a higher-boiling cryogen onto a surface cooled by a
lower-boiling cryogen can also cause a hazardous situation. Liquid air dripping
onto equipment can cause cold embrittlement (see Chapter 3). Typically, the outer
shell or vacuum jacket of a cryogenic storage Dewar is not intended to experience
cryogenic temperatures. Consequently, the outer shell is usually fabricated of
carbon steel, which is not a material suited for low-temperature service. When large
liquid-hydrogen Dewars are filled, there can be cold vent gases for a long period
oftime. Under this circumstance, there can be liquid air dripping off the vent lines,
and if this condensate is allowed to drip onto a carbon steel outer shell, or on steel
plates, the resulting thermal contraction can give rise to stress which can fracture
the embrittled structure. In the case of a Dewar, the loss of vacuum will result in an
increased boil-off rate, which might present a secondary safety hazard. There have
been occurrences that have caused the failure of materials by cold embrittlement.
The venting of cold hydrogen gas has cracked carbon steel deck plates on a barge
and, in another case, the carbon steel vacuum jacket on a liquid-hydrogen storage
Dewar. The cold vent pipes are also a hazard to personnel if physical contact with
them is possible. Where the vent pipes or other cold equipment could be touched,
or where condensate could form in copious amounts and fall where it is not wanted,
it will be necessary to insulate, externally, the vent pipes through the distance where
damage could occur. If there is no danger of cryogenic frostbite to personnel, it is
possible to catch and divert the condensate by draining it to a place where it can
evaporate harmlessly.
If cold transfer lines or vent pipes are allowed to exist in places where they
could be inadvertently contacted by operating personnel or bystanders, serious
frostbite or cryogenic bums can result.
Condensation 77

6.2. PREVENTIVE MEASURES

Unwanted condensation of substances within cryogenic systems can be pre-


vented by first purging these substances from the system before cooling it down to
operating temperatures and then preventing their subsequent entry into the system.
(Purging is discussed in Chapter 7.) When the system has been purged and the
degree of purge has been verified, the next step is to keep the internal pressure above
that ofthe external atmosphere. If this is not possible, leakage of air into the system
must be prevented (see Chapters 7 and 10). In a cryogenic system being maintained
at a pressure below that of the external atmosphere and at a temperature below the
condensation temperature of air, the detection of air intrusion is very difficult.
Vacuum spaces are also vulnerable and require protection with the provision
of pressure relief valves (see Chapter 5). Frequently, this type of protection can be
incorporated into the evacuation port valve.
Where external condensation is a problem, the piping or equipment must have
thermal insulation applied to the exterior. This must be done wherever the cold
surface can be inadvertently contacted by personnel or where condensed air can
cause a hazard by falling on equipment that can become embrittled or inoperative
or where the dripping liquid that is enriched in oxygen can cause the formation of
a combustible or explosive mixture.

REFERENCES
I. Honig, R. E., and Hook, H. O. (1960). RCA Review 21,360.
2. Edeskuty, F. J., Reider, R., and Williamson, K. D., Jr. (1971). Safety, in Cryogenic Fundamentals
(G. G. Haselden, ed.), pp. 633--672, Academic Press, New York.
3. Croft, A. J. (1971). Cryogenic fluids, in Advanced Cryogenics (C. A. Bailey, ed.), Chap. 2, Plenum
Press, London.
4. Edeskuty, F. J. (1979). Safety, in Hydrogen: Its Technology and Implications (K. E. Cox and K.
D. Williamson, Jr., eds.), Vol. IV, Chap. 5, CRC Press, Boca Raton, Florida.
5. Stewart, R. B., and Johnson, V. J. (1961). A Compendium of the Properties of Materials at Low
Temperatures (Phase II), WADD Technical Report 60-56, Part IV, United States Air Force,
Wright-Patterson Air Force Base, Dayton, Ohio.
Chapter 7

Combustion Hazards

One of the most feared hazards in any system is that of unwanted combustion. The
possibility of fIre and explosion is a legitimate cause for concern and for additional
attention to system safety. Although carbon monoxide, as well as oxygen and condensed
air (see Chapter 9), can present a combustion hazard, here we will be concerned with
liquid hydrogen and, to a lesser extent, with liquefIed natural gas (LNG).

7.1. FIRE PREVENTION

In order for a combustion to occur, three elements must be present: a fuel, an


oxidizer, and an ignition source. In the control of combustion hazards, the effort is
made to eliminate the possibility of two of these three elements existing in the
presence of the third. In principle, this does not sound difficult, but complications
can arise in practice.

7.1.1. Ignition Sources


First, there is the need to eliminate ignition sources. Although the relatively
high ignition temperature of hydrogen-air mixtures does make some ignition
sources incapable of starting a fIre, the very wide range of hydrogen 's flammability
and its low ignition energy mitigate this advantage. As with all combustibles, the
existence of open flames, welding, smoking, and other obvious ignition sources
must be prohibited near the storage of combustible cryogens or wherever flamma-
ble mixtures can exist. However, this is not enough. Frequently, there is a need for
electronic or electrical equipment in the vicinity of cryogenic storage. When this
equipment could possibly be the source of an ignition, additional measures must
be taken to ensure the safety of the system. When possible, the electrical equipment
should be built so as to be "intrinsically safe." This means that the total energy
available within the case of the equipment at any time will be less than the minimum
ignition energy of the stored cryogen. The very low ignition energy of a
stoichiometric mixture of hydrogen and air (0.02 mJ) makes this a very stringent
requirement for many applications.
79
80 Chapter 7

If intrinsically safe equipment is not available, the next possibility is to use


equipment that is explosion proof (EP). The term "explosion proof' means that the
equipment is capable of withstanding a combustion or explosion within the case of
the instrument without causing ignition of any combustible gas mixture surround-
ing the instrument. Thus, not only must the case be sufficiently strong to withstand
the pressure generated by the internal combustion, it must also have sufficient
structural integrity so that any gap in the enclosure still has a smaller dimension
than a minimum distance that has been called the maximum experimental safe gap
(MESG).i The MESG is smaller than the quenching gap (see Table 8.1) because in
this instance the flame inside the case ofthe instrument could be under an elevated
pressure caused by the combustion within the case. Equipment meeting the above
requirement is rated within the National Electric Code rating as Class 1, Division
1 or Division 2 , Group B. Class 1 is for combustible vapors; Division 1 is for a
normally dangerous location, and Division 2 is for areas outside of the location where
the combustible vapors would normally exist; and Group B includes hydrogen?
If equipment that does not meet either of these first two qualifications is
required in an area where a combustible gas mixture could exist, a third alternative
is possible. The equipment can be placed in a purged box that is maintained under
a positive pressure with an inert gas (typically nitrogen).
Even if the above measures are successful, the possibility of other ignition
sources still exists. It is often impossible to preclude the existence of a small particle
of sand, dust, welding slag, or other impurity within the cryogenic system, particu-
larly if the system is large and field-fabricated. During the venting of gas or rapid
two-phase flow, any loose, solid particles that are present can be entrained in the
flow. This venting can result in rather high velocities. Under some circumstances,
sonic velocities can be approached. One way in which this could occur is venting
to the atmosphere from a source at a pressure somewhat above 2 atm. During the
flow the pressure drop to the outside atmosphere will be distributed along the flow
path. However, upon the closing of a valve, just before a valve is closed to stop the
flow, the entire system pressure drop must occur across the valve seat. If the
upstream pressure is of the order of twice, or greater, that of the downstream
pressure, sonic flow can occur. If a particle flowing at that velocity strikes a pipe
wall, say, at a right-angle bend in the pipe, it can be stopped, and its translational
energy will be converted to heat. A small particle flowing at close to sonic velocity
does not have quite enough energy to raise its temperature to the ignition tempera-
ture if the energy is uniformly distributed throughout the entire particle. However,
at the moment of impact, the energy will not be equally distributed, and under this
circumstance, it is possible for the impact area of the particle to be heated to the
ignition temperature of the adjacent gas mixture in the case of air impurities.
Another possible source of ignition is the accumulation of a static charge of
electricity. The generation of electric charge by flowing hydrogen, without en-
trained solids, has been investigated. 3,4 In the tests performed, some charge accu-
Combustion Hazards 81

mulation was noted in flowing gaseous hydrogen, although not sufficient to cause
an ignition in a hydrogen-air mixture. With liquid hydrogen, the charge accumu-
lation was even smaller.
The degree of electric charge that a flowing fluid can accumulate is determined by
its electrical conductivity. If the liquid has a conductivity of greater than W- IO 0- 1 cm- I ,
the charge that can arise from the ionization of the fluid can also dissipate. If, on
the other hand, the liquid has a conductivity less than 10-15 0- 1 cm- I , the buildup
of a charge is less likely. It is mainly with fluids that have conductivities between
these extremes that static charge accumulation is usually expected.
The electrical conductivity of liquid hydrogen has been measured5 and found
to be in the neighborhood of 10-19 0- 1 cm- I . Therefore, the accumulation of an
excessive electric charge might not be expected. However, if a charge does build
up, the very low conductivity ofthe liquid hydrogen will prevent rapid dissipation
of that charge.
There are ways in which a greater electric charge could build up within flowing
liquid hydrogen. Any type oftwo-phase flow could result in a charge accumulation
that could be very much larger. During the transfer of liquid hydrogen, two-phase
flow is commonly experienced, especially during the cool-down phase ofthe flow.
Another possibility is the presence of solid particles, either from solid impurities
that were not properly cleaned from the system or from higher-boiling gases that
have been condensed to a solid. The transfer of slush hydrogen is guaranteed to
involve solid particles, and the possibility of electric charge buildup should be
further investigated (see Chapters 10 and 12).
In the case of a solid particle entrained in flowing fluid, an electric charge can
be accumulated as it proceeds down the pipe. The energy accumulated equals
(CeV;)/2, where Ce is the capacitance of the particle and Ve is the accumulated
voltage. If a particle with an equivalent diameter of 1 mm accumulates a charge of
1.5 x 10---9 C (equivalent to 27 kV), it will have an electrical energy of 0.02 mJ. A
pressurized gas can sustain this magnitude of electrical stress, 6 and this energy is
sufficient to ignite a stoichiometric hydrogen-air mixture.
In the case of an unwanted ignition during gas flow, often it is not possible to
identify the ignition source. However, the total elimination of ignition sources from
static electricity and flowing particles is very difficult under field conditions. This
is another reason to strive for the highest possible level of cleanliness in cryogenic
systems.

7.1.2. Elimination of Combustible Mixtures


Once one has done everything possible to eliminate ignition sources, the next
task is to prevent the occurrence of combustible mixtures. This involves avoiding
the creation of a combustible mixture when first filling the system, preventing an
unwanted release of the combustible gas into an oxidizing atmosphere, and pre-
82 Chapter 7

venting the intrusion of air into the cryogen space. Although the release of a
combustible cryogen is necessary in the case of Dewar venting, either for depres-
surization, pressure relief, or normal boil-off, this type of venting will be done under
controlled conditions and will be discussed later (Section 7.2).

7.1.2.1. Protection against Leakage

One way in which a combustible gas could be released is by a leak from the
system. This situation is more insidious because its onset cannot be predicted and
because the leak could occur in a number of different places. The leak does not
necessarily catch fire, but if it does, in the case of hydrogen, the resulting flame is
almost invisible in daylight. In the dark, a yellow-to-orange flame is usually visible.
In daylight it is possible to see heat patterns around the flame, but these are more
easily visible only if one is able to observe the area around the shadow of the vent
where the flame is erupting. In the case of a large leak that ignites, a concern is in
the possibility of personnel inadvertently entering the flame. Numerous sources
have suggested the technique of carrying a broom in front of the body so as to have
the burning of the more easily ignited bristles serve as an indicator of an unseen
flame. Another concern is the possible accumulation of a large mixture of combus-
tible gas with air in the range of combustibility, and the cloud then encountering an
ignition source.
The first line of defense against leaks is to have a leak-tight system that has
been carefully leak-tested under all operating conditions and maintained leak-free.
This includes both ambient-temperature and cold leak testing at operating pressure.
Second, combustible-gas-monitoring detectors with responding alarms should be
placed at appropriate points throughout the system. The obvious placement for a
leak detector is right above the point where the leak will develop. If there are some
places where a leak is more likely to develop, a detector should be placed there.
However, it is not always possible to predict where a leak could develop, and so
the question arises as to where the detectors should be placed. This is a strong
argument for the use of multiple detectors.
There are three mechanisms by which a leaking gas can spread throughout an
external volume. These are diffusion, buoyancy, and convection currents. Although
hydrogen has a high diffusion coefficient, diffusion velocity for hydrogen will be
in the neighborhood of a few centimeters per second. On the other hand, with
ambient-temperature hydrogen gas, buoyancy will cause upward velocities of a few
meters per second. As indicated in Chapter 1, convection currents are less predict-
able, can vary considerably, and can be much faster. Nevertheless, in the absence
of strong convection currents, the location of one of the combustible-gas detectors
should be above the apparatus being monitored. Where convection currents are
present, return air intakes are an additional location to be considered. This is another
reason that it is best not to rely on only one combustible-gas detector. 7
Combustion Hazards 83

Any system leakage that is detected must not be allowed to persist. Initially,
the system must be clean and leak-tight. The system must be fabricated with
materials that are not susceptible to cold embrittlement (or hydrogen embrittlement
in the case of hydrogen systems). Maintenance must be of high quality and well
documented. System instrumentation must include detection devices and alanns.
Overstresses must be avoided, and periodic retesting and recertification according
to ASME code is a good idea.
A common source of leaks in a previously tight system is through the seat of
a shutoff valve. For a gas system, the use of either a ring-and-blank flange or a
double-block-and-bleed system (shown in Fig. 7.1) is a good way to ensure that the
leaking of a shutoff valve does not allow the leakage to proceed into parts of the
system where it can cause damage. For a cryogenic fluid, neither of the above two
systems appears practical because of the requirement for vacuum j acketing in most
instances. For cryogenic service, the ring-and-blank flange would be difficult to
install and to operate. For the double-block-and-bleed system, a line that is open to
the atmosphere and is connected to the cold volume could present the hazard of air
condensation (see Chapter 6). For vacuum-jacketed systems, an alternative is
sometimes possible. Ifthere is a second valve downstream ofthe shutoff valve, the
volume contained between the two valves will be fitted with a relief valve (see
Chapter 5). As shown in Fig. 7.2, this section of line can usually be fitted with an
additional opening leading to a source of an inert gas (helium in the case of
liquid-hydrogen storage and nitrogen for LNG). The inert-gas pressure in this
volume can then be maintained at a pressure higher than that of the upstream
pressure during shutdown times. In this manner, ifthe shutoff valve should develop

Fig. 7.1. Hydrogen shutoff systems: (A) ring


A
and blank; (B) double block and bleed. 8 The
ring-and-blank flange is shaped like a figure
eight, with one of the circles being a solid disk,
and the other having a hole the size of the pipe
inner diameter to allow full fluid flow when
inserted in the flow stream. In the case of the
double-block-and-bleed system, normal flow
operation is with the two line valves open and

=======~=======
the vent valve to the atmosphere closed. When
all three valve positions are reversed, any B
leakage through the upstream line valve will
be vented to the atmosphere rather than flow-
ing further downstream.
84 Chapter 7

Low Pressure
Regulated ---j)IcJ--t---t-I
Helium Supply

Sample_-DI<}-----'
Port

Fig. 7.2. Helium-block technique for a hydrogen shutoff system. 8 If one of the liquid-hydrogen shutoff
valves leaks, helium would leak into the Dewar, preventing liquid hydrogen from leaking out.

a small leak, the leak will be of the inert gas into the combustible cryogen storage
space, rather than of the out-leakage of the combustible fluid. 8

7.1.2.2. Purging
The previous discussion was concerned with the creation of unwanted com-
bustible mixtures that could result from an outflow or leakage of the combustible
cryogen from the cryogenic system. An equally important consideration, especially
in the case ofliquid-hydrogen storage, is the preclusion of the entry of air into the
cryogen storage volume. The first precaution is that of purging the air that remains
in the system after its fabrication or after it has been opened for any reason, such
as maintenance or modification.
Purging can be done by one of several methods, and the most effective method
should be chosen for a given system. F or systems that can be characterized as having
a short length-to-diameter ratio (a sphere would be the ultimate), the system can be
purged by evacuation and back-filled with an inert gas. If the evacuation is
sufficiently complete, the combustible gas can be directly admitted to the storage
volume. However, depending upon the process, either safety or operational con-
straints may require a more complete purge than merely one that reduces the air
Combustion Hazards 85

content below the flammable range. Any air remaining in the system after the purge
process is completed will condense to a solid upon contact with liquid hydrogen
and consequently present a hazard. Thus, it is possible that the purge process would
have to be repeated until a satisfactory condition is attained. As with all purging
operations, the degree of purge should be verified by gas analysis before proceed-
ing.
With some systems it might not be possible to ensure that leakage would not
occur when the system is at a pressure below that of the external atmosphere. Also,
some systems might not be able to withstand a total evacuation, although for most
vacuum-jacketed systems, this will not be the case. For such systems, an alternative
purging method is to pressurize the system with an inert noncondensable gas, allow
the gases to mix by diffusion (a slow process), and then vent the gas mixture. The
pressure that can be used will be limited by the system safe operating pressure, and
this method will obviously require repeated purge cycles until a satisfactory purity
level is attained.
For systems that can be characterized as having a large length-to-diameter ratio
(such as a pipeline), a flow-through purge with an inert gas is usually preferable. It
should be noted that merely flowing an amount of gas equal to the volume of the
pipe is not sufficient to effect a satisfactory purge. Several pipe volumes are
required.
In all purging operations, as mentioned above, the quality of the purge should
be verified by subsequent gas analysis. Furthermore, attention should be given to
dead-end locations. For either of the latter two methods of purging a dead-end
volume, it is possible to push the residual gas to the end of the pipe and then let it
merely expand back into its original volume. For the evacuation and back-fill
method, care must be taken that there is no leakage into the system during the time
the system is below ambient pressure. For some systems, a combination of purging
methods may be necessary.
Once the system is safely purged, the combustible cryogen can be admitted to
the system. After this is achieved, it is desirable to maintain the system at a pressure
above that of the surrounding atmosphere. This positive pressure should be suffi-
ciently great that a positive pressure with respect to the atmosphere will be
maintained through any variation of the external atmospheric pressure that could
occur. The difference in pressure should also be large enough that its presence is
readily ascertainable with the pressure monitors on the system. If the pressure of
the cryogenic system were to drop below the ambient pressure, the possibility
would exist for leakage of air into the system. This occurrence can be especially
hazardous in the case of the storage of liquid hydrogen, because the air will
condense within the storage Dewar to a solid, which will give no indication of its
presence. In this way, massive amounts of solid air could accumulate. Although it
would still require an ignition source to start any reaction, the resulting mixture can
be hazardous.
86 Chapter 7

In most cases there will not be any problem in maintaining a positive pressure
on the storage Dewar. However, this is not true for the storage of slush hydrogen.
One of the most pervasive safety problems in handling slush hydrogen is that its
vapor pressure is only about 7 kPa (52 Torr), and thus slush-hydrogen systems are
likely to be subatmospheric in pressure. Slush hydrogen is discussed later (Chapter
10).
In some instances, after the completion of an operation, post-run purging to
remove combustible gas from a system is required. This would be the case for some
maintenance operations or long periods of inactivity. As before, gas analysis is
required to determine the effectiveness of the purge. Also, it is necessary to ensure
that there is not enough leakage of air into the system during the initial part of the
post-run purge to create a combustible mixture within the enclosure at any time. In
addition, precautions must be taken to ensure that no residual combustible gas could
remain within the interstices of porous material or in dead ends of the system. The
post-run purge could start either with evacuation or with flushing of the system with
an inert gas before introduction of air. Again, the success of the purge must be
verified.
Another possible cause of an unwanted combustion can occur when starting
the evacuation of a system containing a combustible gas. If the vacuum pump is
initially filled with air and then the pump starts to evacuate a system filled with
hydrogen or methane (natural gas), the resulting mixture will pass through the
combustible range. An even greater hazard can result if the vacuum pump is
evacuating more than one system at the same time (not recommended). In that case
the mixture in the pump lines might always be in the combustible range. A similar
hazard could exist where the vent systems from more than one cryogenic storage
volume are interconnected. Explosions in vent systems have occurred, and in one
case an explosion occurred in a vent line carrying the boil-off from a liquid-hydro-
gen Dewar. In this case, more than one system was connected to a vent system that
was being flared (see Chapter 12). Fortunately, no serious damage was done, but it
was a reminder that it is a good idea to provide independent vents and evacuation
systems for every system carrying combustible fluids.

7.2. RELEASE OF COMBUSTIBLE GAS TO THE ATMOSPHERE

In most installations that handle combustible gases, it will be necessary to vent


some of the gas, either occasionally, intermittently, or, in some cases, continuously.

7.2.1. Un flared Venting


For low flow rates, the combustible vapors corning from a liquid-hydrogen
storage Dewar are seldom flared or burned. No insulation is perfect, and therefore
the maintenance of a temperature gradient across an insulation space requires a
Combustion Hazards 87

corresponding heat flux. Consequently, the long-term storage ofliquid cryogens is


almost always accompanied by the evolution of boil-off gas. Although the boil-off
process can be interrupted, the time for doing so is limited, and eventually the
venting process must be resumed. The factors that affect the rate at which the
pressure will rise in a closed-off Dewar are discussed in Chapter 5. In the case of
the combustible cryogens, assuring the safety of the venting gas requires additional
attention.
Obviously, the venting gas must not be allowed to accumulate to dangerous
quantities, and the gas must not be vented into closed or restricted volumes such as
closed rooms or under eaves. When venting of cold gas produces a visible vapor
cloud, the extent of the cloud is not a reliable indication of the extent of the gas that
is within the range of combustibility. The size of the vapor cloud depends upon the
humidity in the surrounding atmosphere and can be either larger or smaller than the
combustible region.
The venting from a liquid-hydrogen storage Dewar is usually done through a
vent stack with its top above any nearby structure and sufficiently tall that the
venting hydrogen combustible plume will not come near personnel, the ground,
any vulnerable object, or any ignition source or building. The stack must also be
sufficiently tall that an inadvertent ignition of the vented gas (such as by lightning)
will not cause injury to people, secondary fires, or damage to equipment near the
base ofthe stack. The top must be protected from rain or snow with a flapper valve
or a tee section on the pipe. The normal boil-off quantity for a hydrogen Dewar is
of the order of a few grams per second, and the length of the combustible plume
for such a rate is no more than about one meter. Furthermore, the venting gas will
have warmed somewhat in passage through the uninsulated vent stack to the point
that it will have some positive buoyancy and will tend to rise upon leaving the top
of the stack. During a liquid-hydrogen-filling operation, the vent flow rates will be
higher, and the vapors colder. Under this circumstance the vapor plume can be
parallel to the ground for a few meters before beginning to rise, and a noticeably
longer vapor plume can be observed.

7.2.2. Flared Venting


For the low venting rates mentioned above, flaring (or burning) the vented
vapors is seldom necessary. The vented hydrogen can easily and safely be dispersed
in the local atmosphere. Some experimental operations have required much higher
venting rates (as high as many kilograms per second in some cases). In these cases
it is usually necessary to flare the venting hydrogen, and this has been done at
several installations. Two methods have been used to flare safely a larger flow of
hydrogen effluent. One such method is to use a flare stack with a gas seal (see Fig.
7.3).8 In this device the back-diffusion of air is restricted, and very low flows are
successful in keeping the flame volume at, or above, the top of the stack. At the
88 Chapter 7

tg",,,,. r

Fig. 7.3. Hydrogen flare stack. s

high end of the flow range, up to 100 kg of hydrogen per second have been safely
vented and flared.
The flare stack is very effective and usually will burn almost all of the vented
gas. Flare stacks are used in a number of different applications such as LNG/lique-
fied petroleum gas (LPG) terminals, coal gasification plants, chemical plants, and
refineries. Each application is different and requires the appropriate flare stack to
meet the individual requirements. In addition to flow rate, gas combustion charac-
teristics, and temperature, the stack design must also consider prevention of air
entry into the volume of the stack, igniter design, the possible consequence of the
thermal radiation from the flame, and flame stability.9,]O The latter consideration
includes effluent velocity as well as wind direction and velocity. With improper
design, the flame might be able to lift off the top of the stack and in some cases
Combustion Hazards 89

Fig. 7.4. Hydrogen burn pond at Kennedy Space Center. Water has been drained for maintenance of
the plumbing.

even be extinguished, or the combustion volume could retreat into the stack or flash
back into it. Flare stacks are effective and safe if they are properly designed,
operated, and maintained.
Another method of flaring that has been used successfully is the burn pond
(see Fig. 7.4). In this case the hydrogen is piped under the surface of a water pond
to a header and then into a horizontal distribution system feeding vertical pipes
coming out of the water surface. Each of the vertical pipe outlets is capped with
a loose-fitting cap that just dips into the water surface and deflects the hydrogen
back to be released under the water to bubble up and bum just over the water
surface.
A precautionary note worth mentioning is that the aspiration of air into an
opening in the upstream portion of the vent system must be avoided. If this were
to occur, the air influx could give rise to a combustible mixture within the vent
system and cause a flash back into the system, which could either damage the
system or even result in a flame issuing from the opening. However, both of the
above types of flare system have been used successfully. They can operate over a
wide range of flow rates, and they can be turned off or on as required.
90 Chapter 7

7.2.3. Venting versus Flaring


The above discussion oflow flow rates of venting hydrogen that do not require
flaring, and high flow rates that do, raises the question as to the flow rate crossover
point at which flaring becomes desirable. For some experimental facilities, flow
rates on the order of 115 gls (0.25 Ibis) have been mentioned. Unfortunately, there
is no universal answer to this question. The limit to flow rate for an unflared venting
of hydrogen will depend upon the total hydrogen inventory that can accumulate
within the combustible plume, the distance to which the plume can extend, the
available exclusion area, and local terrain and atmospheric conditions. This deci-
sion must be made for each individual situation. In some cases the question is
answered by operational considerations in that, during nonoperational periods, the

80

60

g
-=c:
C>
Q)
....I
"0
:::l
B
.240
u
Q)
:c
'til
:::l
.D
E
8
20
D

50 100 150 200


Hydrogen Release Rate (g/s)

Fig. 7.5. Combustible cloud length as a function of hydrogen release rate. 12 Curves A and B are for
nighttime releases with wind velocities of I and 3 mis, respectively. Curves C and D are for daytime
releases with wind velocities of I and 3 mis, respectively.
Combustion Hazards 91

venting rates are only the few grams per second of normal Dewar venting, and
flaring is not required. During operational periods, the rates might be so high that
flaring of vented hydrogen is obviously necessary.
The possibility of a large unflared release ofliquid hydrogen or cold hydrogen
gas has received some study. 10, 11 The distance to which a combustible cloud can
extend depends upon the venting flow rate, the temperature of the venting gas, and
the local wind velocity and turbulence. Unfortunately, the presence ofa vapor cloud
does not necessarily indicate the limits of a combustible mixture. 10 Hydrogen gas
at one atmosphere and 20.3 K has a slightly negative buoyancy. Spill tests ofliquid
hydrogen have shown that most ofthe warming ofthe hydrogen is caused by mixing
ofthe hydrogen with the local atmosphere. 11 Once the plume becomes buoyant, the
rise rate and rise angle will be along the resultant vector of the buoyancy and wind

100

,
, ,
A,'
,
80 ,
,
, ,
~ ,
, ,
, ,
"C
;;;,

8 , ,

, "
,
~ 60
'iii ,
.B ,
,
E ,
8.5 ,
, , ,
, B, , ,
,,
-- -
,
~ 40 ,
::z: ,
5i ,
,
~
~
,
,
,
~
J:
, ,,
~

V
20
,
,
I

,
,
--
0
-
o --
, , '~
o 50 100 150 200
Hydrogen Release Rate (g/s)

Fig. 7.6. Mass of hydrogen in a combustible cloud as a function of hydrogen release rate. 12 Curves A
and B are for nighttime releases with wind velocities of I and 3 mis, respectively. Curves C and Dare
for daytime releases with wind velocities of I and 3 mis, respectively.
92 Chapter 7

velocity vectors. Some calculations have been made to predict the length of a
combustible plume, the hydrogen inventory in the plume, and the height to which
the plume can rise. 12 (See Figs. 7.5-7.7.) It should be pointed out that these
calculations have been made for a release of hydrogen gas at a temperature of20 K,
and the only set of data against which they can be checked was taken for the release
of liquid hydrogen. This is an area where more safety analysis is needed (see
Chapter 12).
Atmospheric electric discharges, like lightning, can cause the gas from a
nonflared vent stack to ignite. It is not necessary for the lightning to strike the stack;
it need only strike within one or two kilometers. This phenomenon has been

10~----------~---------.----------.---------~

g
III
a:
E 6
:::J

.~
:;
'0
:::J
.2
(,)
Q)
jS 4
1ii
:::J
.0
E
8
2

50 100 150 200


Hydrogen Release Rate (g/s)

Fig. 7.7. Maximum rise of a combustible cloud as a function of hydrogen release rate. 12 Curves A and
B are for nighttime releases with wind velocities of I and 3 mis, respectively. Curves C and D are for
daytime releases with wind velocities of 1 and 3 mis, respectively.
Combustion Hazards 93

observed on a number of occasions. Although the fire is not necessarily dangerous,


it is usually extinguished. The vent stack can be provided with a helium gas purge.
Normally, the helium gas is valved off. A fire at the top of the stack will probably
not be noticed in the daytime. However, at night it is quite obvious as a pale yellow
flame, often about 30 cm (1 ft) long. The procedure for extinguishing the fire is as
follows. First, a slow flow of helium gas with the hydrogen flow up the stack is
started. This does not extinguish the flame. Next, the hydrogen flow is valved off,
stopping the hydrogen flow and extinguishing the flame. The helium flow is
continued for about five minutes (or long enough to cool any metal that has been
heated by the fire until its temperature is below the hydrogen ignition point). Then
the hydrogen flow is reintroduced before terminating the helium flow. The whole
procedure can take less than 10 minutes. Ifa flapper valve has been used at the top
of the stack, it will be necessary to inspect any closure gasket to see if the flame
has damaged it to the point where it should be replaced.

7.3. FIRE PROTECTION AND RESPONSE

Hydrogen/air fires do not present the hazard of toxic fumes and smoke that
other fires do. However, this will not be true if other combustible materials are
involved in the fire. This is one reason why good housekeeping practice does not
allow the presence of combustible materials in the vicinity of hydrogen systems.
As mentioned previously, the difficulty of seeing the flame can be an added hazard.
The occurrence of a fire causes changes in the surroundings that can be used
to detect the fire. These changes have been called the signature ofthe fire. Although
the nonluminous hydrogen flame makes visual detection difficult, there is a strong
heat effect and also turbulence of the surrounding atmosphere. Both of these
phenomena can be used in fire detection. 13 However, in a system in which there is
a large number ofplaces where leakage could occur, the fire detection system should
be capable of monitoring a large area over considerable distances.
The installation of a fire-water system in conjunction with liquid-hydrogen
storage has both advantages and disadvantages. Furthermore, there are two types
of water systems to consider: (1) a fixed spray over the tank and (2) a hydrant with
a hose.
The spray or deluge system is intended to protect the Dewar from external heat
sources (such as a fire in the fill or discharge connections). The purpose of the water
is to keep the Dewar cool to preclude a secondary safety problem that could arise
from an external fire overheating the Dewar's outer shell. The major concern is the
possibility of a buildup of pressure leading to rupture of the Dewar, causing a
boiling-liquid-expanding-vapor explosion (BLEVE). It should be remembered that
the Dewar is already protected against external heat by a vacuum jacket and the
intervening insulation. In any case, it is of utmost importance that water not be
94 Chapter 7

sprayed on the Dewar's vent system. If water were to impinge upon any part of the
vent system, flow paths could become blocked with ice, or relief devices could be
rendered inoperative, thus leaving the Dewar without a safe way to vent the normal
boil-off gas and allowing a dangerous buildup of pressure. If this were to occur, it
could be the cause of the very event that the water was supposed to prevent, a
BLEVE. In a few cases where large external heat fluxes from other sources have
been anticipated, fire-water spray systems have been installed. However, in many
cases this type of protection is not installed. There is a reluctance to allow water in
the vicinity of the Dewar because of the possibility of entry of the water into the
Dewar vent system with consequences as described above (see Section 13.2.1.3).
The second type of fire-water system would be a hydrant and hose installation
to offer cooling protection to equipment in the vicinity of the Dewar for use in the
case of a fire at the Dewar. The water requirement would be set by the nature of the
equipment to be protected. In general, gas storage cylinders, extraneous equipment,
and combustible materials should be kept away from liquid-hydrogen storage
Dewars. In the case of hydrogen being stored in a closed space special precautions
are recommended, including a limitation to the quantity of hydrogen stored, a
sprinkling system, and a pressure-relieving (blowout panel) area. In the case of a
hydrogen fire, the fire-water system must not be used to extinguish the fire. The
fire should be extinguished by shutting off the supply of hydrogen. To extinguish
the fire without stopping the supply of hydrogen will create the possibility of the
accumulation, and later ignition, of a larger combustible mass, with even more
disastrous consequences.
A decision to provide a fire-water cooling system would have to be made with
specific knowledge of the involved system. Although there may not be a universal
requirement for the provision of fire-water protection at a given location, it should
be remembered that local authorities, such as fire chiefs or facility safety officials,
have the authority to impose additional requirements and should always be kept
informed of the operations and emergency procedures that might be required. Their
input and cooperation should be sought. They should also be given any training
that they desire concerning the nature of the installation. Whenever possible, the
response to an emergency situation should be according to preplanned procedures.

7.4. COMBUSTION ACCIDENT CAUSES AND CONSEQUENCES

When the safety precautions designed to prevent unwanted combustion fail,


the consequences can be drastic and tragic and are often spectacular. The LNG
storage vessel rupture and subsequent fire in Cleveland in 1944 resulted in 128
deaths and over 200 injuries. Devastation was widespread, and one consequence
was a delay of decades in the further development of the LNG industry and the
general public's continued distrust in the safety of LNG. 10 The fire on the hydro-
Combustion Hazards 95

gen-filled dirigible Hindenburg, although not as catastrophic as the LNG fire in


Cleveland (65 of the approximately 100 people on board the Hindenburg survived
the accident), has left a similar distrust in the safety of hydrogen. 14
The requirements of the U.S. space program have led to a large-scale liquid-
hydrogen production and distribution industry. Although not totally without inci-
dent, this technology has had an enviable safety record for more than four decades.
This record is largely the result of (I) the understanding of the potential hazards
that preceded the development and (2) the attention to the training of involved
personnel. The largest hydrogen liquefaction facilities have production capabilities
of approximately 55,000 kg (60 tons) per day, with the total U.S. liquefaction
approaching 180,000 kg (200 tons) per day. Deliveries in 106-m3 (28,000 gallon)
rail tank cars have been made over a 3,200-km (2000 mile) distance. Deliveries in
highway trailer-mounted Dewars in 49-m3 (13,000 gallon) quantities are common,
and delivery can be made anywhere in the 48 contiguous United States with no
venting of product during the delivery trip. Although highway accidents have
occurred, these have rarely resulted in the loss of hydrogen.
Most of the relatively few accidents and incidents that have occurred have been
at user sites. Ordinis summarized 96 accidents involving liquid hydrogen at NASA
sites up to the end of 1974 and found that about 87% of the mishaps were the result
of errors in operation, procedures, design, or planning. The remainder of the
mishaps were caused by malfunctions, material failure or incompatibility, or
contamination. In about two-thirds of the mishaps, an ignition ofa hydrogen release
occurred, and in 30% of those cases, the ignition source was unknown. Of the five
highway accidents that had occurred, two were caused by rupture disk failure and
three were vehicle accidents.

7.4.1. Blast Overpressure


The consequences of an unwanted, confined combustion include fire and
possibly shrapnel and blast waves. For unconfined combustion of hydrogen in air,
many hydrogen releases have shown that a simple deflagration results (see Chapter
8). In some ofthese cases overpressures have resulted, but these were small, usually
ofthe order of7 kPa (1 psi) or less. However, there have been reports of explosions
from outdoor releases of hydrogen. The consequences of overpressures are shown
in Table 7.1, which shows that an overpressure of 7 kPa (1 psi) is sufficient to knock
down personnel. 14

7.4.2. Thermal Radiation


The thermal radiation from the combustion of a cloud of a mixture of gaseous
fuel and air can, upon reaching a given point, cause secondary fires or burns to
personnel. However, the thermal flux can be significantly reduced by the interven-
ing atmosphere depending upon the amount of water vapor in the air.
96 Chapter 7

Table 7.1. Physiological Effects of Blast OverpressureQ

Maximum overpressure
[kPa (psi)] Effect on personnel
7 (1) Knock personnel down
35 (5) Eardrum damage
100 (15) Lung damage
240 (35) Threshold for fatalities
345 (50) 50% fatalities
450 (65) 99% fatalities

Q Ref. 14.

Thermal radiation burns to personnel are a potential hazard from fIres involv-
ing combustible cryogens such as hydrogen or LNG. Human skin consists of two
main layers, the epidermis or outer layer, which is about 0.1 mm thick, and the
derma, a deeper layer 1 to 2 mm thick. 16 In a fIrst-degree burn, little or none of the
derma is destroyed. In a second-degree burn, all of the epidermis and a signifIcant
part of the derma are affected, and in a third-degree burn, all of the epidermis and
derma are destroyed. Experiments on pig skin, which closely resembles human skin
in its response to burns, have shown the effects of heat fluxes and duration of
exposure in causing burns.
Hardee and Lee l6 have correlated burn data to obtain the relationship between
the duration of the burn period and the amount of heat that must be absorbed by the
skin to produce second- and third-degree burns. These data are for a heat source at
a temperature in the vicinity of the combustion temperatures of hydrogen--air
(2318 K) and methane-air (2148 K) mixtures. 1 These data have been plotted in Fig.
7.8 to show the incident heat rate that can cause second- and third-degree burns as
a function of exposure time.
Two of the possible scenarios for a combustion are: (1) a release resulting in
a combustible cloud with delayed ignition forming a hemispherical or spherical
fIreball; and (2) a release with immediate ignition forming a flame approximating
a vertical inverted cone.
To compute the heat incident rate at a distance, Rfo from a combustion, it is
necessary to know the rate of energy radiated from the flame, and consequently, its
energy release rate, and the fraction of the combustion energy that is released as
radiation. This fraction has been given as 17-25% for hydrogen--air combustion
and 23-33% for methane-air flames. 1
At any given distance from the flame, the heat flux can be determined from
the total radiant energy evolution rate divided by the area of the surrounding sphere
at the distance under consideration. For a combustible cloud that has lifted off the
Combustion Hazards 97

10.-------------~------------~----------__;

0.1 -+--........- .....................,....,.....,...,...j--.,....---.---.-.,.........,....,....+--........-,........,..........,....,..........-j


0.1 10 100
Exposure Time (s)

Fig. 7.8. Second- and third-degree skin burn thresholds. 16

ground, this can be approximated as a sphere, so at distance Rfi the area is equal to
41tR}. For a fireball, the burning duration can be approximated by dividing the cloud
dimension by the velocity of the flame (see Chapter 8). The rate at which radiant
heat is incident on a given area can then be estimated by dividing the total radiation
energy at distance Rf by the time of duration of the flame. For a continuous flame,
such as with a massive leak, the rate at which heat radiation reaches a subject can
be computed from the product of the rate ofleakage times the energy of combustion
times the fraction of combustion energy emitted as radiation divided by the above
area factor. The duration of the fire will be determined by the time that the leak is
allowed to persist.
For exposure to hydrogen flames of no more than 30-s duration, a distance of
55 m (180 ft) has been calculated to be sufficient to prevent second-degree burns
98 Chapter 7

from exposure to hydrogen-air combustion for most quantities of hydrogen.


However, this distance depends upon the water vapor content of the intervening
atmosphere. For comparison purposes, under the same circumstances, the equiva-
lent distance for a hydrocarbon flame would be 206 m (675 feet).!7
It should be pointed out that hydrogen fires from a finite release are of short
duration. First, at any given time, the fraction of the hydrogen from a spill that is
within the combustible range of concentrations is small! [in one instance, out of
about 900 kg (2000 lb) of hydrogen released in 25 s, only about 10% was burned
in the combustion!8]. Second, the duration, d (in seconds), of a hydrogen fire has
been given! as

d = 0.47(wi /3

where Wfis the mass of fuel in kilograms. A spill of 1.9 m 3 (500 gallons) of liquid
hydrogen was observed to bum for less than one minute. While this is not a precise
enough piece of data to serve as a check on the above equation, it must be
remembered that the flame time is also controlled by the evaporation rate. In any
case, hydrogen fires from a finite release are short-lived compared to fires due to
conventional fuels, and this fact has led to the conclusion that liquid hydrogen is a
safer fuel than conventional aircraft fuels in many instances. 19 This conclusion is
based upon the short burning time for heat transfer into the fuselage in a survivable
crash.

7.4.3. Protection from Combustion Accidents


The most widely accepted separation distances for liquid-hydrogen storage
Dewars from occupied buildings and other structures are those given by the
National Fire Protection Association (NFPA).2o For quantities of liquid hydrogen
up to 22,000 kg (75,000 gallons), the largest required distance to any of the
structures listed is 30.5 m (100 ft). However, these isolation distances are for the
routine storage of liquid hydrogen to serve only as a source of hydrogen as a gas
to commercial establishments. In this type of storage there is less likelihood of an
accident such as failure of the vessel caused by overpressure, and only routine
operation is expected.
With larger experimental facilities, especially if liquid oxygen or other pow-
erful oxidizers are also present and used in the same experimental programs, other
mechanisms for accidents can exist. The question of what distance from the storage
of liquid hydrogen is a safe distance in experimental facilities handling large
quantities and using it at high rates has been investigated in several cases, unfortu-
nately without very much agreement. 2! One such investigation has given separation
distances for avoiding injury to personnel by either thermal radiation, overpressure,
or shrapnel.! The data are presented in Fig. 7.9. These distances can be shortened
Combustion Hazards 99

1x106~------------------------------~--------________-,

Experimental

i Areas

:i<Il 1x103
~
Qi
:::>
u..
Fire, Thermal Radiation
(Inhabited Buildings,
Undiked)

lx10i-------~~-.--~~L---~r_~----~~,_--~--~--~
1 10 100 1,000 10,000
Distance, RI (m)

Fig. 7.9. Quantity-distance relationships for the protection of personnel near liquid-hydrogen storage
and experimental areas (unbarricaded).l

if personnel are in appropriately designed protective structures. This is an area


where further study would be helpful (see Chapter 12).
For facilities that use or store combustible cryogens, the training of the
operating and safety personnel must include a complete knowledge of the fire
hazard and the measures taken for prevention. They must also be aware of the
necessity to avoid quick fixes without a complete knowledge of the possible
consequences. The ingenuity of a well-meaning but inadequately trained employee
can lead to an accident.
The general public already has an inordinate fear of hydrogen and LNG. Thus,
it is incumbent upon designers and operators of systems containing combustible
cryogens to be extra careful in the design, construction, and operation of this type
of system.
100 Chapter 7

REFERENCES

1. Hord, J. (1976). Is Hydrogen Safe?, National Bureau of Standards Technical Note 690, Institute
of Basic Standards, National Bureau of Standards, Boulder, Colorado.
2. National Fire Protection Association (1962). National Electric Code, Article 501-Class I
Locations, N:ational Fire Protection Association, Quincy, Massachusetts.
3. Cassutt, L., Biron, D., and Vonnegut, B. (1962). Electrostatic hazards associated with the transfer
and storage of liquid hydrogen, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.),
Vol. 7, pp. 327-335, Plenum Press, New York.
4. Arthur D. Little, Inc. (1961). Final Report, Electrostatic Hazards Associated with the Transfer and
Storage of Liquid Hydrogen, Contract AF 18(600}-1687, Arthur D. Little, Inc., Cambridge,
Massachusetts.
5. Willis, W. L. (1966). Electrical conductivity of some cryogenic fluids, Cryogenics 6 (October),
279.
6. Willis, W. L. personal communication.
7. Chelton, D. B. (1964). Safety in the use ofliquid hydrogen, Chapter 10 in Technology and Uses
of Liquid Hydrogen (R. B. Scott, W. H. Denton, and C. M. Nicholls, eels.), Chap. 10, Pergamon
Press, Oxford.
8. Edeskuty, F. J. (1979). Safety, in Hydrogen: Its Technology and Implications (K. E. Cox and K.
D. Williamson, Jr., eds.), Vol. IV, Chap. 5, CRC Press, Boca Raton, Florida.
9. Straitz, J. F. III (1987). Flare technology safety, Chem. Eng. Prog. 83(2}, 53--62.
10. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
11. Witcofski, R. D., and Chirivella, J. E. (1984). Experimental and analytical analysis of the
mechanisms governing the dispersion of flammable clouds formed by liquid hydrogen spills, in
Proceedings ofthe World Hydrogen Energy Conference IV (T. N. Veziroglu, W. D. Van Vorst, and
J. H. Kelley, eds.), Pergamon Press, Elmsford, New York.
12. Stewart, W. F., Dewart, J. M., and Edeskuty, F. J. (1990). Safe venting of hydrogen, in Hydrogen
Energy Progress VIII (T. N. Veziroglu, ed.), Pergamon Press, New York.
13. Custer, R. L. P., and Bright, R. G. (1974). Fire Detection: State-Of-The-Art, NASA Lewis Research
Center Report NASA CR-134642, Cleveland, Ohio.
14. Bowen, T. L. (1975). Investigation of Hazards Associated with Using Hydrogen as a Military Fuel,
Naval Ship Research and Development Center Report 4541, Bethesda, Maryland.
15. Ordin, P. M. (1974). Review of hydrogen accidents and incidents in NASA operations, in
Proceedings ofthe Ninth Intersociety Energy Conversion Engineering Conference, pp. 442--453,
American Society of Mechanical Engineers, San Francisco, California.
16. Hardee, H. C., and Lee, D. O. (1977178). A simple conduction model for skin burns resulting from
chemical fireballs, Fire Res. 1, 199.
17. Weintraub, A. A. (1965). Control of Liquid Hydrogen Hazards at Experimental Facilities, Health
and Safety Laboratory Report HASL-160, U.S. Atomic Energy Commission, New York.
18. Reider, R., Otway, H., and Knight, H. T. (1965). An unconfined, large-volume hydrogen/air
explosion, Pyrodynamics 2, 249-261.
19. Brewer, G. D. (1991). Hydrogen Aircraft Technology, CRC Press, Boca Raton, Florida.
20. National Fire Protection Association (1994). Liquefied Hydrogen Systems at Consumer Sites,
National Fire Protection Association Report NFPA 50B, Quincy, Massachusetts.
21. Edeskuty, F. J., Reider, R., and Williamson, K. D., Jr. (1971). Safety, in Cryogenic Fundamentals,
(G. G. Haselden, ed.), Chap. 11, Academic Press, London.
Chapter 8

Combustion Properties

Under the right circumstances, almost any property of a substance can relate to its
safety. However, there are a number of properties that directly relate to the
possibility of a fire or explosion hazard when dealing with combustible cryogens.
In this chapter we will discuss these properties as they pertain to hydrogen and
methane [including liquefied natural gas (LNG)].
Table 8.1 lists some properties of interest in the discussion of safety for
hydrogen and methane and compares them with those of gasoline. 1,2

8.1. DEFLAGRATION

With hydrogen or methane, as with many other flammable gases, with the
proper conditions, combustion can occur in either of two different ways, deflagra-
tion or detonation. A simple combustion, or deflagration, occurs when a portion of
a gas mixture, within a combustible composition range, is heated to its ignition
temperature. At this point combustion commences, and the heat released is suffi-
cient to raise the temperature of the adjacent gas mixture to its ignition temperature.
The reaction can thus propagate through the mixture in the form of a flame front
that can travel throughout the extent of the combustible mixture. The rate of this
reaction is controlled by heat transfer, and deflagration flame velocities are of the
order of a meter per second.
The limits of flammability in air define the range of gaseous fuel concentra-
tions in air at which the homogeneous mixture will be capable of being ignited and
will propagate a deflagration flame. These limits are usually determined experi-
mentally by observing the upward propagation of a flame in a vertical tube. 1 In a
gravitational field, buoyancy exerts an influence, with the result that flame propa-
gation in a downward direction is more difficult than upward propagation. Conse-
quently, near the fuel concentration limits for combustion as described above, the
combustion usually will not be complete throughout the combustible mixture. For
a more narrow concentration range, combustion can proceed in any direction, and
101
102 ChapterS

Table S.l. Combustion Properties of Hydrogen, Methane, and Gasolinea,b

Property Hydrogen Methane Gasoline


Flammability limits (vol %) 4.0--75.0 5.3--15.0 1.0--7.6
Detonability limits (vol %) 18.3--59 c 6.3--13.5 1.1-3.3
Minimum ignition energy (mJ) 0.02 0.29 0.24
Autoignition temperatured (K) 793--1023 903--1493 501-744
Flame temperature (K) 2318 2148 2470
Burning velocity (cm/s) 265-325 37-45 37-43
Detonation velocity (km/s) 1.48--2.15 1.39-1.64 1.4-1.7
Diffusion velocity (cm/s) <2.0 < 0.51 < 0.17
Buoyant velocity (m/s) 1.2-9 0.8--6 Nonbuoyant
Quenching gap (mm) 0.64 2.03 2.0
Maximum experimental safe gap (mm) 0.08 1.2 0.7
Stoichiometric compositionb (%) 29.53 9.48 1.76

a Refs. I and 2.
b In mixtures with air at conditions of 10 1.325 MkPa (l atm) and 294 K (70 OF).
C For low-energy initiation; see Section 8.3.

d A range is necessary for this value because the autoignition temperature depends upon the ignition method. The values
for hydrogen and methane are taken from Ref. 2.

then combustion will approach completeness. More complete combustion for


hydrogen-air mixtures begins to be approached at about 8 vol % hydrogen.
As shown in Table 8.1, the flammability limits of methane are wider than those
of gasoline, and those of hydrogen are much wider than those of either methane or
gasoline. This is usually taken to indicate that gasoline is the safest of these three
fuels, with methane or LNG being the next safest, and hydrogen being the least
safe. Under some circumstances this may be the case. However, a more realistic
comparison must take into account all of the properties as well as the circumstances
of the combustion. Gasoline vapors are heavier than air, diffuse slower, and burn
slower, thus lengthening the duration of a dangerous situation. Furthermore,
exceeding the lower flammable limit is frequently what enables the onset of a
combustion. As shown in Table 8.1, the low limit of combustible concentrations
for gasoline is lower than either that of methane or that of hydrogen and, in this
respect, might be of greater concern for gasoline than for either of these other fuels.
The minimum ignition energy in air is the minimum spark energy that is needed
to ignite the most easily ignitable concentration offuel in air. The minimum ignition
energies for methane and gasoline are more than 10 times greater than that of
hydrogen, which is only 0.02 mJ. Several times this amount of electrical energy
has been shown to be generated by the act of a person removing a coat of synthetic
material. 3 Thus, the low ignition energy is a major contributor to the concerns about
hydrogen's safety.
Combustion Properties 103

The diffusion velocity of a gas in air depends upon the temperature, T, and
varies as T 312. For this reason, the cold gases originating from spills of cryogenic
fuels will diffuse more slowly than these same gases at ambient temperature. From
Table 8.1 it can be seen that, at ambient temperature, hydrogen will diffuse about
4 times faster than methane and about 12 times faster than gasoline.
The buoyant velocities of the gaseous fuels represented in Table 8.1 vary with
bubble size and are also strongly dependent upon the temperature of the fuel gas.
However, in this case the velocity estimates were made for ambient-temperature
gas and for buoyant masses of a specific size. Hence the buoyant velocities listed
in Table 8.1 are useful mainly for demonstrating their relative values. Hydrogen's
higher diffusion velocity and buoyancy make it easier for hydrogen to reach greater
distances more quickly but also contribute to its ability to dissipate to below
combustible limits more quickly. When all of the properties in Table 8.1 are
compared, it becomes evident that it is not possible to rank these fuels according
to safety, because various possible accident scenarios can illustrate situations in
which anyone of these fuels will be the safest or the most hazardous.
The autoignition temperature in air is shown in Table 8.1 as a range. The reason
for this is that this temperature depends upon the method of ignition. Hansel et al. 2
give this temperature for hydrogen and methane for three different types of ignition:

Q)
:0
<U c:
E 0
E .0>
~~
c:
o
Z

Fig. 8.1. Effects of temperature and pressure on flammability limits. 4 LFL, Lower flammability limit;
UFL, upper flammability limit.
104 ChapterS

mixture heated in a glass vessel, mixture contacting a heated Nichrome wire, and
mixture heated by a laminar-flow air jet. Heating in a glass vessel gives the lowest
ignition temperature, and the heated Nichrome wire gives the highest ignition
temperature. For the ignition of a drifting combustible cloud, the Nichrome wire
value would seem the most appropriate.
In general, the properties shown in Table 8.1 are dependent upon the local
conditions. Figure 8.1 shows that the flammability limits of a combustible gas vary
with temperature and pressure. As either pressure or temperature is decreased, the
flammability range is narrowed. In the case of pressure decrease, at a sufficiently
low pressure, the upper and lower limits coalesce, with the result that below this
pressure no mixture of fuel and air is combustible (see Fig. 8.1).
The behavior of the combustibility range is shown in a different way in Fig.
8.2, where it can be seen that as the total system pressure is lowered, the minimum

10,------r-----,------r-----~----~----~----~

~>-
~
G)
c
W
c
.Q
:1::
C
!1'
E
::J
E
'2
~ 0.1

101 kPa

0.01 +--...--+-~-+_---.-_I_-...--_+-~-+____.-_+-....._____l
o 10 20 30 40 50 60 70
Hydrogen Concentration (vol%)

Fig. 8.2. Effects of pressure and composition on the minimum ignition energy for hydrogen in air.4 The
conditions represented by the areas under the curves do not result in ignition, but in the area above the
curves, ignition can occur.
Combustion Properties 105

ignition energy (MIE) for hydrogen-air mixtures increases. 4 From Fig. 8.2 it also
can be seen that the minimum ignition energy is a strong function of the actual
composition of the mixture, reaching its minimum value near the composition of a
stoichiometric mixture. The stoichiometric mixture is that mixture for which the
quantity of fuel and oxidizer are in the correct proportion so that after the combus-
tion is complete, none of the fuel or the oxidizer remains (for an Hrair mixture,
this is 29% H2), both being completely consumed and replaced by their combustion
products.
For a mixture of methane and air, Fig. 8.3 shows the large increase in
combustibility range caused by increasing the oxygen content of the air in the
mixture. 4 For hydrogen-air mixtures, Fig. 8.4 shows the effect of replacing the
nitrogen in the air with other inert gases. As seen in Fig. 8.4, the substitution ofthe
nitrogen by argon results in easier ignition, indicated by a lower ignition energy,
whereas the substitution of nitrogen by either carbon dioxide or helium raises the
minimum ignition energy requirement. 4
For combustion proceeding through a tube, the flammable limits for hydro-
gen-air mixtures are also affected by the total system pressure as well as by the
tube diameter. Figure 8.5 shows that as pressure is lowered, the combustion range
is narrowed and that as tube diameter is decreased, the minimum pressure for
combustion to occur is raised. Figure 8.6 shows the widening of the combustible
range for methane in air as the temperature increases. Compilations of combustion
properties of hydrogen and other combustible gases are given in Refs. 4--6.

100
50

10
~ 5
>-
e'
Q)
c 1
w
c 0.5
.2
.~
c
!l' 0.1
E
~ 0.05
E
c
~ 0.01
0.005

0.001
0 10 20 30 40 50 60
Methane Concentration (vol%)
Fig. 8.3. Effect of mixture composition on the minimum ignition energy ofmethane-oxygelHlitrogen
mixtures. 4 The conditions represented by the areas under the curves do not result in ignition, but in the
area above the curves, ignition can occur.
106 ChapterS
1.0 ....-----r-----,---.-----,-----.------.,...------,

0.5

~
>-
e>
CD
c:
W
c:
....
.Q
c:
0.1
SP
E
::l
E
c 0.05
~

0.01 -t----.--t--.....---+-...,..--f-........-+----.--+--.---+--.-----4
o 10 20 30 50 60 70
Hydrogen Concentration (vol%)

Fig. 8.4. Minimum ignition energy for hydrogen in 21 % oxygen with various di1uents. 4 The conditions
represented by the areas under the curves do not result in ignition, but in the area above the curves,
ignition can occur.

The results of experiments to date indicate that hydrogen-air mixtures in any


proportion will not undergo detonation if completely unconfined (see Section 8.2).
If the speed of the combustion wave remains close to the initial velocity, in the
neighborhood of a meter or so per second, appreciable overpressures would not be
expected in the open atmosphere. However, some flame acceleration and associated
overpressures have been noted. For a hydrogen release in which about 91 kg
(200 lb) of hydrogen was estimated to participate in the subsequent combustion, a
deflagration velocity of 30 m/s was detected. This velocity is about 10 times that
noted in Table 8.1 and about two orders of magnitude lower than that ofa detonation
(see Section 8.2 and Chapter 13). In this case an overpressure ofless than 2.3 kPa
(0.34 psi) was estimated.?
Combustion Properties 107

1,OOO~-----....,.....------.--------r-------.

500

100

50

as
a..
C
! 10
~ 5
!
a..

1.0

0.5

0.1-+----....,....----l---....,.....---4----.----+---..,.--~
o 20 40 60 80
Hydrogen Concentration (vol%)

Fig. 8.5. Effects of pressure and tube diameter on the flanunability limits ofhydrogen in air.4 Flammable
mixtures are represented by the areas above the curves, and nonflanunable mixtures by the areas below
the curves.

On the other hand, confined deflagrations can build up substantial pressures,


sufficient to cause considerable damage. The photograph in Fig. 8.7 shows the
damage to a lightly constructed shed that experienced an internal, initially confined,
hydrogen-air deflagration. In this case the pressure rise was sufficient to cause the
rupture of the eardrums of a person within the enclosure at the time of the ignition.
As shown in Table 7.1, this would indicate an overpressure in the vicinity of35 kPa
(5 psi).8 Because of the light construction, the deflagration did not remain confined
when the walls were blown off, resulting in effective pressure reliefwithin the shed.
For a completely confined deflagration, either a hydrogen-air or a methane-air
mixture of uniform concentration, starting at 1 atm and ambient temperature, will
reach a maximum pressure multiplication of a factor of about 8 for near-
stoichiometric mixtures. I ,9 Figure 8.8 shows the pressure multiplication as a
function of hydrogen concentration in air for the initial conditions mentioned
above. The solid curve is for an adiabatic, isochoric, complete combustion (AleC).
108 Chapter 8

100

80
/n3K

/
/"
l,..--523K
/ l,..--293K
60
'iii
Q.
C
!!?
:::l Rammable
gj
!!? Region
I

I))
Q.
40

20 ~\
~"
\ ~/'
/
o
o 4 8 12 16
Methane Concentration (vol%)

Fig. 8.6. Effect of temperature on the flammability limits for methane in air.4 Flammable mixtures are
represented by the areas above the curves, and nonflammable mixtures by the areas below the curves.

For this theoretical case, the combustion is complete, and the entire energy release
from the combustion is consumed in heating the reaction products and residual
gases. Because the reaction is completely confined, the increase in temperature is
accompanied by a pressure increase.
Actually, the Alec curve is never quite reached. Amore typical result is shown
in Fig. 8.8 by the dotted curve, which lies below the Alec curve for several reasons.
First, below 4% and above 75% hydrogen, the mixture is not within the combustible
range, so there is no combustion and, consequently, no pressure rise. Second, from
about 4% up to about 8% hydrogen, combustion takes place only in the upward
direction, and combustion is incomplete in this concentration range. Above 8%
hydrogen, the combustion can proceed in any direction, and the actual reaction
Combustion Properties 109

Fig. 8.7. Shed damage caused by hydrogen-air deflagration. (Photograph courtesy of the Los Alamos
National Laboratory.)

curve starts to rise to approach the AICC curve. Third, during the finite time of the
combustion, there is time for some heat transfer from the combustion products to
the containment walls and solid objects within the enclosure. This process removes
some of the combustion energy and decreases the pressure that is attained.
The heat capacity of the containment, and the solid objects within it, is usually
much greater than that of the combustion products, with the result that during a
confined hydrogen-air deflagration the pressure can be expected to rise rapidly over
a short interval of time (on the order of a fraction of a second to a few seconds,
depending upon the size of the containment vessel) and then decrease as heat
transfer continues, until the pressure decreases to become close to the original
pressure (over a period of tens of seconds to minutes, again depending upon vessel
size). This behavior has been confirmed by confined-combustion tests in a closed,
vertical cylindrical vessel with a diameter of 2.13 m and a height of 5.18 m. 10 Tests
performed in a larger vessel (l7-m sphere) have also verified this behaviorY
Pressure relief panels are effective in minimizing pressure increases in experimental
rooms where deflagrations are possible. The initially confined hydrogen combus-
tion in the light shed shown in Fig. 8.7 illustrates the efficacy of pressure relief for
hydrogen-air deflagrations. Investigations of the pressure rise during deflagrations
in vented enclosures and within nonuniform mixtures (gas pockets) have been
carried out and are discussed in Refs. 12 and 13.
110 ChapterS

V
8
~

0:
6 / ~
~
~
!

J
]i 4
.1::
c::
~
~

III
!
0-
iii
c::
iI:
2

~- - -
I
I
I
I

0
0 20 40 60 80
Hydrogen Concentration (vol%)
Fig. 8.8. Theoretical maximum pressure multiplication resulting from the confined combustion of
hydrogen--air mixtures. 9 The solid line shows the theoretical maximum pressure ratio (final pressure/in-
itial pressure) resulting from the adiabatic, isochoric (constant volume), complete combustion (AICC)
of hydrogen-air mixtures. Initial conditions are 101.325 kPa (l atm) and 293 K. The dotted line is
illustrative of a possible approach to an AICC. The degree of approach will depend upon the specific
reaction conditions. However, the pressure ratio given by the AICC curve will never be fully attained
because some energy will be lost from the combustion products to the walls of the containing vessel
and other solid objects that are present.

8.2. DETONATION

A combustion reaction that is more vigorous than a defiagration can occur if


a shock wave results within the combustible mixture. The shock wave must be
sufficiently strong to heat the reactants to their ignition temperature. If so, the
reaction will proceed at the speed of the shock wave. This is a much faster reaction,
and rather than the defiagration speeds of up to a few meters per second, the
detonation speed will be well over 1 kmls. A comparison of these two modes of
combustion is given in Table 8.2.
Combustion Properties 111

Table 8.2. Comparison ofthe 1\vo Types of Hydrogen Combustion

Property Deflagrati on Detonation


Energy transport mechanism Heat transfer Shockwave
Velocity (mls) 2.7 1500
Maximum pressure ratio ga b

Pressure relief effective Yes Noc

a Ratio of final pressure to initial pressure for a confined, stoichiometric hydrogen-air mixture, initially
at 1 atm and ambient temperature.
b For a hydrogen-air detonation starting at 1 atm and ambient temperature, a pressure multiplication by
a factor of at least 15 can be expected. However, detonation can result from a transit from deflagration
to detonation, with the possibility that the initial pressure is already increased by the previous
deflagration. In addition, reflection of shock waves can increase instantaneous local pressures, with the
result that pressure multiplication factors as high as 120 have been given in the literature (Ref. 1).
C In a detonation, pressure can rise too quickly to allow a pressure relief system to function effectively.

A hydrogen-air combustion can start as a detonation, or it can start as a


deflagration and then transit to a detonation after the flame has traveled for some
distance. As shown in Table 8.1, the composition range in which a detonation can
take place is narrower than that for deflagration. The commonly quoted range for
detonation in a hydrogen-air mixture is from 18.3% to 59% hydrogen. However,
with higher-energy ignition sources, these limits can be extended, and this is
discussed in Section 8.3. The factors that influence whether hydrogen-air combus~
tion will occur as a detonation, rather than a deflagration, include the hydrogen
percentage, the strength of the initiator, either complete or partial confinement of
the reaction, and the presence of structures that can induce turbulence in the flame
front. For the combustion to start as a detonation, an energetic source of initiation
is required.
F or a deflagration to transit to detonation, a mechanism to accelerate the flame
velocity is necessary. Factors that favor this transition include the composition
being within the detonation range, a degree of confinement, and anything that can
induce turbulence in the flame front as it travels through the combustible mixture.
The latter tends to stretch out the flame front and increase its velocity.

8.3. DETONATION STUDIES

An important parameter in initiating a detonation is the strength of the initiator.


The more energetic the ignition source, the more likely is the possibility of
combustion starting as a detonation. Studies of the initiation of detonation of
hydrogen-air mixtures have been made in which the energy of the initiator has been
varied. Detonations were studied in a 3D-m-long channel with a rectangular cross
section 1.83 m wide and 2.44 m highl4 and in a heated tube, 13 m long with a
112 Chapter 8

100,--r------r--------.--------.---------r--------,

E
.
.<
~
1i
E
III
i5 10
~c:
0
iic:
~
0

14-----~--_r----~---+----~---+----~--~----~--~
10 20 30 40 50 60
Hydrogen Concentration (vol%)

Fig. 8.9. Detonation cell diameter for a hydrogen-air mixture initially at room temperature and
atmospheric pressure. 16

circular cross section with a 43-cm diameter. 15 These studies showed that the
detonation occurs along a series of detonation cells. The smaller the dimension of
the cell, the more likely it is that detonation will occur. Detonation cell sizes were
measured by the traces left on a sooted foil, lining the floor of the test chamber. The
cell size varied with hydrogen concentration, with a minimum cell size occurring
near the stoichiometric mixture. Figure 8.9 shows a plot of the cell size versus the
hydrogen concentration. 16 For these experiments, high explosives were used to
initiate the detonations. Figure 8.10 shows the amount of explosive needed to
initiate the detonation as a function of hydrogen concentration. 16
Although this type of initiation strength will not be available in most cases, it
is of interest to note that with the use of such high-energy initiators, the range of
the detonability of hydrogen-air mixtures at 20C has been extended down to
Combustion Properties 113

\
50,000

\
10,000

\ /
~ 1,000
.9
CD
~
8
.~

V
1\1 100
~ \
!
1\ /
\ /
10

1.0 /
0.5
10 20 30 40 50 60
Hydrogen Concentration (vol%)
Fig. 8.10. Critical mass of explosive (grams of Tetryl) to initiate detonation in hydrogen-air mixtures
initially at room temperature and atmospheric pressure. 16

11.6% and up to 74.9% hydrogen by volume. 15 These studies have also determined
some useful parameters that determine whether a detonation can persist in various
geometric configurations. Some of these relationships are presented in Fig. 8.11,
which shows that for a detonation to persist in a tube with a circular cross section,
the inside diameter must be at least one-third of the cell dimension. In the case of
two wide parallel plates, the distance between the plates must be at least equal to
the cell dimension. In each case in Fig. 8.11, the geometric parameter must be at
least as large as the function of the cell size shown in the figureY
Because of the higher pressure multiplication and the rapidity of the pressure
increase, detonations are much more destructive than deflagrations. This was
illustrated by experiments involving confined hydrogen combustions in a 6.4 m by
4 m by 4.1 m (21 ft by 13.1 ft by 13.5 ft) enclosure constructed of massive concrete
114 ChapterS

(","rT)=====~FF~==========:n-'omin=
T
Aft,
Propagation Down a Cylinder

Wmin =A

Propagation Down a Two-Dimensional Channel

oT ~
Dmin=13A Round
Tube

.L
D Dmin = 11 A Square
Tube

TL
I Wmin =11 A
T
......W-id-e-Ch-a-n-ne-I....

Transmission from a Tube into a Large Open Space


"Critical Tube Diameter"

Fig. 8.11. The effect of geometry on propagation of detonation waves. is For each of the configurations
depicted, the minimum size for detonation to persist is given as a function of the detonation cell
dimension, which is a function of the mixture composition (see Fig. 8.9).

blocks on three sides and the top and closed on one side by a plywood panel. During
deflagrations in which less than 30 L of liquid hydrogen was spilled from a
cylindrical Dewar and ignited, the plywood panel was shattered and blown out, but
the concrete blocks were not disturbed. During a test in which 40 L was spilled and
ignited, a detonation occurred that pushed the blocks aside and the plywood was
not only blown out but was also shattered into much smaller pieces. In addition,
Combustion Properties 115

the higher pressure, caused by the detonation in the test cell, collapsed the liquid-
hydrogen Dewar. 17 Motion pictures taken of these experiments show the greater
destructive power of the detonation. However, these pictures also demonstrate that
confined deflagration can also be destructive.

REFERENCES

I. Hord, J. (1976). Is Hydrogen Safe?, Cryogenics Division, Institute for Basic Standards, National
Bureau of Standards, Boulder, Colorado.
2. Hansel, J. G., Mattern, G. w., and Miller, R. N. (1993). Safety considerations in the design of
hydrogen-powered vehicles, Int. J. Hydrogen Energy 18(9), 783.
3. Cheiton, D. B. (1964). Safety in the use of liquid hydrogen, in Technology and Uses of Liquid
Hydrogen (R. B. Scott, W. H. Denton, and C. M. Nicholls, eds.), Chap. 10, Pergamon Press,
Oxford.
4. Benz, F. J., Bishop, C. v., and Pedley, M. D. (1988). Ignition and Thermal Hazards of Selected
Aerospace Fluids, NASA Lyndon B. Johnson Space Center, White Sands Test Facility Report No.
RD-WSTF-OOOI, Las Cruces, New Mexico.
5. Coward, H. F., and Jones, G. W. (1952). Limits of Flammability of Gases and Vapors, U.S. Bureau
of Mines Bulletin 503, U.S. Government Printing Office, Washington, D.C.
6. Zabetakis, M. G. (1965). Flammable Characteristics of Combustible Gases and Vapors, U.S.
Bureau of Mines Bulletin 627, U.S. Government Printing Office, Washington, D.C.
7. Reider, R., Otway, H., and Knight, H. T. (1965). An unconfined, large-volume hydrogen/air
explosion, Pyrodynamics 2, 249.
8. Bowen, T. L. (1975). Investigation of Hazards Associated with Using Hydrogen as a Military Fuel,
Naval Ship Research and Development Center Report 4541, Bethesda, Maryland.
9. Sherman, M. P., Baer, M. R., and Griffiths, S. K. (1981). Deliberate ignition and water fogs as H2
control measures for Sequoyah, Proceedings of the Workshop on the Impact of Hydrogen on Water
Reactor Safety, Albuquerque, New Mexico, January 26-28, 1981, Vol. IV, pp. 85-124, Sandia
National Laboratory Report NUREG/CR-20 17, SANDSI-066IAN.
10. Torok, R., Siefert, K., and Wachtler, W. (1983). Hydrogen Combustion and Control Studies in
Intermediate Scale, Electric Power Research Institute Report EPR! NP-2953, Palo Alto, Califor-
nia.
II. Edeskuty, F. J., Haugh, J. J., and Thompson, R. T. (1986). Safety aspects oflarge-scale combustion
of hydrogen, in Hydrogen Energy Progress VI (T. N. Veziroglu, N. Getoff, and P. Weinzierl, eds.),
pp. 147-158, Pergamon Press, New York.
12. Cubbage, P. A., and Marshall, M. R. (1972). Pressures generated in combustion chambers by the
ignition of air-gas mixtures, in Chemical Engineering Symposium Series, No. 33, pp. 24-31,
Institute of Chemical Engineers, London.
13. Sibulkin, M. (1982). Pressure rise generated by combustion of a gas pocket, Combustion Flame
38,329.
14. Sherman, M. P., Tieszen, S. R., and Benedick, W. B. (1989). The Effect ofObstac1es and Transverse
Venting on Flame Accelerations and Transition to Detonation for Hydrogen-Air Mixtures at Large
Scale, Report NUREG/CR-5275, SAND85-1264, Sandia National Laboratories, Albuquerque,
New Mexico.
15. Stamps, D. w., Benedick, W. B., and Tieszen, S. R. (1991). Hydrogen-Air-Diluent Detonation
Study for Nuclear Reactor Safety Analysis, Report NUREG/CR-5525, SAND89-2398, Sandia
National Laboratories, Albuquerque, New Mexico.
116 ChapterS

16. Lee, J. H., Knystautas, R., Guirao, C. M., Benedick, W. B., and Shepherd, J. E. (1982).
Hydrogen-Air Detonations, Proceedings of the Second International Conference on the Impact
of Hydrogen on Water Reactor Safety, pp. 961-1005, Sandia National Laboratories Report
NUREG/CP-0038, EPR! RP 1032-35, SAND 82-2456, Albuquerque, New Mexico; see also
Guirao, C. M., Knystautas, R., and Lee, J. H. (1989). A Summary of Hydrogen-Air Detonation
Experiments, Sandia National Laboratories Report NUREG/CR-4961, SAND87 -7128.
17. Zabetakis, M. G., Furno, A. L., and Perlee, H. E. (1963). Hazards in Using Liquid Hydrogen in
Bubble Chambers, U.S. Bureau of Mines Report oflnvestigations 6309, U.S. Department of the
Interior, Bureau of Mines, Washington, D.C.
Chapter 9

Oxygen Hazards

As a cryogen, liquid oxygen (LOX) is a light blue, odorless, transparent liquid.


LOX is not shock sensitive and does not decompose. However, it is a strong oxidizer
and will vigorously support combustion.
Like other cryogens, LOX does present the hazard of causing pressure buildup
if confined (see Chapter 5). On the other hand, it does not present the hazard of
diluting the air and creating an atmosphere that will not support life. However, its
presence in a concentration higher than normal presents other hazards. Although
the breathing of oxygen has an exhilarating effect, breathing a concentration of 60%
or more can produce lung damage, and an extended exposure to an atmosphere of
pure oxygen can cause bronchitis, pneumonia, or lung collapse. 1 As with other
cryogens, LOX is capable of freezing body tissues (see Chapter 2).
Although oxygen is not a fuel, it still can cause unwanted combustion hazards
because of its influence in enhancing combustion of other substances. Air with an
oxygen concentration of greater than 23% at sea level or with a partial pressure of
over 175 Torr is defined as oxygen-rich. 2 Anything that burns in air will burn more
vigorously in oxygen-enriched air, and even more so in pure oxygen. In many cases,
substances that are considered noncombustible in air will burn readily in oxygen,
and, in other cases, normal combustion can become explosive in enriched or pure
oxygen atmospheres. Teflon has been shown to burn readily in oxygen at elevated
pressure {7 MPa [1000 psi (absolute)]}, and stainless steel has been consumed in
a fire involving liquid oxygen.
Because almost all substances that are not completely oxidized can burn in oxygen,
two of the three ingredients necessary for combustion (oxidizer and fuel) are always
present in oxygen systems. Thus, one cannot overemphasize the importance of elimi-
nating all heat sources that could raise any part of the system to its ignition temperature.

9.1. PROPERTIES OF OXYGEN AND CONSEQUENT HAZARDS

Under the proper conditions of pressure, oxygen can be a liquid over a very
wide range of temperature. The triple-point temperature and pressure are 54.35 K
117
118 Chapter 9

and 0.15 kPa (1.14 Torr), respectively. The critical-point temperature and pressure
are 154.58 Kand 5.04 MPa [731 psi (absolute)], respectively? The density of LOX
at standard atmospheric pressure is 1140 kg/m3 (71.1 Ib/ft 3 ) (see Table 1.1), and
this density limits the quantity that can be transported over the highways because
of weight restrictions. The high density is also a cause for concern in that during
flow of liquid oxygen at a high rate, a rapid closure of a valve could rupture or
damage a pipeline by the resulting "water hammer" effect.
With respect to safety, the greatest concern in the handling of oxygen is its
capability to enhance the speed and vigor of combustion. Although oxygen can be
mixed with combustible substances without reacting, the resulting mixture is easily
ignited and may react explosively in many cases. Another concern is the ability of
oxygen to permeate porous materials, especially clothing, enabling them to bum
much more rapidly when ignited. The presence of substances containing hydrocar-
bons, such as some lubricants and solvents, in either gaseous or liquid oxygen
presents an obvious hazard.
Contaminants in LOX may be in solution, if present in amounts less than that
allowed by the solubility limit. When present to an extent exceeding that limit, the
contaminants will usually precipitate as a solid. The presence of a combustible solid
presents a greater hazard of fire or explosion. Solid hydrocarbons in LOX can react
explosively when subjected to friction, shock, or impact. 3 Most solid hydrocarbon

Table 9.1. Solubility Limit and Lower Flammability Limit of


Hydrocarbons Soluble in LOXa

Solubility Lower flammable


Gas (mol ppm) limit (mol ppm)
Methane 980,000 50,000
Ethane 215,000 30,000
Propane 50,000 21,200
Ethylene 27,500 27,500
Propylene 700 20,000
i-Butane 1,900 18,000
Butene-1 1,000 16,000
n-Butane 860 18,600
i-Butylene 135 18,000
n-Pentane 20 14,000
Acetylene 5 25,000
n-Hexane 2 11,800
n-Decane 0.6 7,700
Acetone 1.5
Methanol 12
Ethanol 15

a Ref. 3.
Oxygen Hazards 119

impurities are less dense than LOX and will tend to float on the liquid surface. They
may give evidence of their presence by forming a ring of solid material around the
interior of the container wall near the liquid surface.
Methane is highly soluble in LOX, and the higher aliphatic hydrocarbons are
less so, with their solubility decreasing as the number of carbon atoms in the
hydrocarbon molecule increases. The solubilities of several hydrocarbons in LOX,
as well as their lower flammability limits, are given in Table 9.1. 3 Most solvents
are solids at the NBP temperature of oxygen.
In addition to the hazard of unwanted combustion, contamination of oxygen
can also make it hazardous or useless in its subsequent application. Fuel cells and
breathing apparatus also have stringent limitations on impurities, and oxygen purity
requirements 3 for these applications are given in Table 9.2.
Contaminants can be introduced in the production of LOX or in its storage,
handling, or use. Exposure to the atmosphere can introduce contamination. Al-
though the major constituents of air might not present any additional hazard, air
frequently contains traces of other substances such as hydrocarbons. Even if present
only in the low parts per million concentration range, such contaminants can
accumulate until they can present a major hazard.
As shown in Table 9.1, acetylene is only slightly soluble in LOX. Acetylene
is a very reactive compound (having a triple carbon--<:arbon bond). For this reason,
its presence in oxygen is generally limited to 0.05 ppm (mole basis) or less. 3

Table 9.2. Oxygen Purity Requirementsa

Requirement

Grade A for fuel cellsb Grade B for breathing


Purity 99.995% 99.60%
Methane 10 ppm 25 ppm
Ethane 2.0 ppm 2.0 ppm
Propane and higher hydrocarbons 1.0 ppm (as propane) 1.0 ppm (as propane)
Alkyne and acetylene hydrocarbons 0.05 ppm (as acetylene) 0.05 ppm (as acetylene)
Total hydrocarbons 14.0 ppm (as methane) 29.0 ppm (as methane)
Moisture 3.0 ppm 3.0 ppm
Nitrous oxide 1.0 ppm l.Oppm
Halogenated hydrocarbons 1.0 ppm 1.0 ppm
Odor No odor No odor
CO and C02 1.0 ppm total 5.0 ppm of each
Particulates 1.0 mg/I (liquid only) 1.0 mg/I (liquid only)

a Ref. 3.
b For Grade A oxygen, all other impurities, including inert gases and nitrogen, not to exceed 30 ppm.
120 Chapter 9

Even noncombustible solid impurities can give rise to hazardous situations by


causing excessive wear or abrasion, ignition of other substances by friction or
impact, interference with moving parts, or plugging of openings leading to instru-
mentation or pressure relief valves.
Oxygen can also react slowly with metals to form their oxides either by film
formation or by corrosion. Corrosion can be chemical, galvanic, or stress corrosion.
Any of these processes can lead to catastrophic failure of a metal under the proper
conditions if any of the following criteria is met:
1. The exposure to oxygen is at a temperature approaching the metal's
ignition temperature.
2. The material forms an oxide with a melting temperature below the expo-
sure temperature.
3. The exposure temperature exceeds the melting point of the base metal.
4. A relatively volatile oxide forms.
5. The specific volume of the oxide is less than that of the base metal, thus
preventing complete coverage of the base metal.

9.2. IGNITABILITY TESTS

If the temperature of a material is raised to its ignition point in an oxygen


atmosphere, rapid combustion of the material will occur. It is often difficult to
determine exact ignition temperatures because the apparent ignition temperature of
a given material is affected by its size and shape (thickness and surface-to-volume
ratio), its heat capacity, its thermal conductivity, its heat of reaction, and the rate of
heat input. Other factors that influence the onset of combustion are the oxygen
pressure and concentration and the exposure conditions. Also, many materials have
local imperfections that may have lower ignition temperatures than the base
material and so can serve as ignitors for the base material. Thus, it is not surprising
that a number of different experimental tests have been developed for determining
the ignitability of various substances in oxygen atmospheres. Ignition and melting
temperatures for a number of metals are given in Table 9.3. 3
There are several methods oftesting a material for sensitivity to reaction with
oxygen. These methods include such tests as mechanical impact, pneumatic impact,
friction, autoignition, and particle impact. 4
The mechanical impact test involves dropping a 9.04-kg (20-lb) weight from
a number of different heights onto a striker pin that rests on the specimen that has
been placed in a cup holding liquid oxygen, liquid air, or one of various mixtures
of liquid air that are enriched in oxygen. 5 Tests may also be carried out with the
oxygen in the gaseous state. In these tests, a material that reacts with oxygen will
explode, flash brightly, or ignite and continue to bum. 6 Tests are performed with
energy inputs of up to 10 kgm. The number of ignited samples in a series of tests
0
Table 9.3. Ignition and Other Pertinent Parameters for Selected Metalsa ~
~
Thennal Reaction
Melting point conductivitl Specific heatb Ignition Heat of reactiond product melting ;:=
N
Metal (K) (W/m-K) Densitl (kg/m3) (J/kg-K) temperaturec (K) (MJ/kgmol) Reaction product point (K) =
a
Aluminum 933 222 2,699 900 >1273 -1670 Ah03 2288 '"
Antimony 904 18.8 6,620 205 923 -697 Sb203 929
Beryllium 1550 146 1,848 1883 1533-2773 -611 BeO
Chromium 2148 66.9 7,190 460 2271 -1128 Cr203 2708
Copper 1356 394 8,960 385 1356 -155 CuO 1599
Iron 1810 75.3e 7,870 460 1583 --S22 F~03 1838
Lead 600 34f 11,360 129 1123-1144 -218 PbO 1161
Magnesium 923 154 1,740 1025 898--913 -602 MgO 3073
Manganese 1518 7,430 481 -385 MnO 808
Molybdenum 2883 142 10,220 276 1018--1053 -544 Mo02
Nickel 1726 92.cf 8,901 439 -244 NiO 2263
Platinum 2042 69.0&" 21,450 131 e PtO 823 h
Silver 1234 418e 10,490 234e 1223 -30.5 Ag20 573 h
Tantalum 3269 54.4 16,600 141 1518--1543 -2092 Ta20s 2073
Thorium 2023 37.i 11,720 142 773 -1222 Th02 3323
Tin 505 62.8e 7,300 226 1138--1243 -581 Sn02 1400
Titanium 1941 15.& 4,507 519 1583-1873 -912 Ti02 2103-2123
Tungsten 3683 166e 19,300 138 1543-1573 --S40 W03 1746
Zinc 692 11Y 7,131 383 1173-1213 -348 ZnO 2248
QRef.3. gAt 17C.
b At 20 C.
h Decomposes.
C Exposed to 0.101325 MPa (I atm) oxygen.
j At 100C.
d Heat of oxide formation.
e At00C. j At-240C.
f At25 C.
N
......
122 Chapter 9

o 2 4 6 8 10
Impact Energy (kgm)
Fig. 9.1. Effect ofliquid-nitrogen dilution on impact sensitivity ofHT-424 adhesive in liquid oxygen
(LOX).6

on the same material, along with the energy input for those ignitions, allows the
material to be ranked according to its sensitivity to oxygen. Samples should be
configured according to ASTM D2512.4 for testing in LOX and according to
ASTM G86 for tests in gas.
Results from the drop test can show the increase in sensitivity that occurs with
increasing oxygen concentration from that in normal liquid air to that in pure
oxygen. This is illustrated in Fig. 9.1, which shows the behavior of an adhesive to
be essentially insensitive to a liquid air with 20% oxygen while at higher oxygen
concentrations the dramatic increase in sensitivity becomes obvious. 6
The pneumatic impact test subjects the sample to be tested to a high-velocity
stream of oxygen, air, or an oxygen-enriched mixture of these fluids. Again, by
Oxygen Hazards 123

varying the composition and velocity of the impacting stream, ignitions can be
noted and comparisons made.
In the friction test, test specimens are fastened to the ends of two hollow
cylinders and rubbed against each other by holding one of the cylinders fixed and
rotating the other cylinder. Test variables include oxygen pressure, loading, and
rubbing velocity. The parameter for ranking the samples is the product of the total
load divided by the area of contact between the two specimens times the velocity
of rubbing.
The autoignition test measures the minimum temperature at which the speci-
men will ignite in oxygen or in an oxygen-enriched atmosphere. The temperature
in the test vessel is increased until ignition occurs.
In the particle impact test, the test specimen is subj ected to a stream of oxygen
containing entrained particles. Ignition conditions permit the ranking of the sam-
ples. 4

9.3. MATERIALS FOR LIQUID-OXYGEN SERVICE

Materials to be used for service in LOX should be selected to be suitable under


the conditions of use. Consideration should be given to the ignition temperature,
the sensitivity to impact in an oxygen atmosphere, possible ignition sources, and
the configuration of use. This requires a knowledge of the material's composition,
ignition temperature, and behavior under exposure to potential ignition sources.
These ignition sources include processes such as mechanical impact, pneumatic
impact, galling of rubbing metals, rubbing friction, adiabatic compression, static
charge accumulation, and electric arcing. Care must also be taken to avoid materials
that would become brittle at the temperature of LOX and then fracture under stress.
Such a fracture could be an ignition source for the base metal or another adjacent
constituent.

9.3.1. Metals
All metals except gold, platinum, and other noble metals are combustible in
oxygen under the proper conditions. Important factors to consider in the use of a
metal in oxygen service include its composition, surface conditions, thermal
characteristics, density, geometry, and physical and mechanical properties. Also of
importance are the characteristics of the metal's oxide coating, such as its compo-
sition, adherence, and density, and the metal's thermal properties, as well as system
and dynamic conditions such as oxygen pressure and temperature, flow velocity,
heat input and removal rate, quantity and intensity of ignition source, and system
cleanliness.
There are many metals that have been safely used in LOX service. The
selection of a particular metal should be made with consideration of the actual use
124 Chapter 9

conditions, such as oxygen pressure, velocity, and temperature. Another considera-


tion is that metal ignition in oxygen service is often caused by a kindling-chain
reaction from the ignition of a polymer or hydrocarbon contaminant.
Nickel and its alloys are very resistant to ignition and combustion. In addition,
they usually have high strengths and significant low-temperature toughness. 4
Stainless steels are relatively resistant to ignition, but, as mentioned above,
ignitions have occurred where either a high pressure or a high flow rate was
present. 4 On one occasion, the failure of a turbine-type flow meter resulted in a fire
in which stainless-steel piping was consumed, and, on another occasion, a thick
stainless-steel flange on the top of a high-pressure LOX Dewar had a hole burned
through it as if it had been cut by a welding torch (witnessed by WFS). In another
incident, the impact or friction caused by the failure of a turbine-type flow meter
started a fire in the stainless-steel discharge piping of a LOX trailer transport. The
truck, tires, fuel, and chassis continued burning until the entire quantity of LOX
available [38 m 3 (10,000 gallons)] was exhausted. Once such a fire starts, the only
recourse is to shut off the oxygen supply, if possible. As long as the oxygen is
present, it will continue to bum everything combustible. 7
Copper is suitable for use in oxygen at all pressures. It is particularly useful
for resisting ignition by particle impact. However, copper and some of its alloys
are combustible when in finely divided configurations such as wire mesh.4

Table 9.4. Combustion Rate for Metal Rods in Oxygen at 1 atm Pressurea

Combustion rate (cm/s) for burning direction:

Materialb Up Down Horizontal


Mild steel 0.76 1.27 1.10
Aluminum 25.4
309 stainless steel 0.43 0.97
316 stainless steel 2.03 0.76
316L stainless steel 0.18
410 stainless steel 0.13 0.61
17-4PH stainless steel 0.30 0.76
4140 stainless steel 0.33 0.15
Nickel" None None
Monel" None None
Inconel" None None
Bronzec None None
Hastelloy 0.15 0.20

a Ref. 3.
b Rods 1.59 mm (1116 in.) to 4.76 mm (3116 in.) in diameter.
C These materials did not propagate combustion in 1 atm oxygen.
Oxygen Hazards 125

Aluminum alloys have been used extensively in flight applications where


weight minimization is important. The use of aluminum alloys in pressure vessels
is attractive because of their high strength-to-weight ratios. However, the use of
aluminum should be avoided where high flow rates, friction, or particle impact
could be encountered. 4
Iron alloys are not good candidates for oxygen service because they can ignite
easily. Although these alloys are used extensively in storage cylinders, they should
be used only where there are no credible sources ofignition. 4 They cannot be used
in LOX service where they become brittle at the temperature of use.
Some metals are not acceptable for oxygen service. Metals to be avoided for
use in oxygen systems include titanium, because of its high sensitivity to impact
and friction, and cadmium and beryllium, because of their toxicity. Beryllium also
has low impact resistance, particularly at low temperature. Magnesium must not be
used where corrosion is possible and also has been shown to be very combustible. 4
Mercury must not be used in oxygen systems because it and its alloys can promote
stress cracking in some metals. Another objection is its toxicity.
Table 9.4 gives combustion rates for selected metals.

9.3.2. Nonmetals
Nonmetals that are often required for use in oxygen systems include such
materials as plastics, elastomers, lubricants, adhesives, and fabrics. In an oxygen
system, the use of nonmetals that are not completely oxidized is a cause for concern
because of their potential for reacting with the oxygen. Compared to metals,
nonmetals have lower ignition temperatures, thermal conductivities, and heat
capacities, and thus they are easier to ignite. The ignition temperature of nonmetals
is highly dependent upon oxygen concentration and pressure.
The low ignition temperatures of polymeric materials make them susceptible
to ignition by the adiabatic compression heating of oxygen upon pressurization. 4
Usually, the heat capacity of the solid part of the system is sufficiently great that it
could absorb the compression heating so that only a small increase in temperature
would occur. However, in the case of rapid pressurization, the heat transfer is
usually far too slow to allow the solid components to absorb the heat. Thus, unless
the compression is done very slowly, the gas being compressed into the storage
cylinder will heat significantly and could reach a sufficiently high temperature to
cause the ignition of some nonmetals. For this reason, it is important that oxygen
systems containing such materials be pressurized slowly.
All polymers will bum in oxygen. Nylon and Mylar are not normally recom-
mended for oxygen service. However, a few nonmetallic materials with higher
ignition temperatures (up to 500C) are resistant to ignition. Polymeric materials
that are most resistant to reaction with oxygen are the fluorocarbon plastics and
elastomers. Elastomers frequently used in oxygen systems are fluorinated com-
126 Chapter 9

pounds such as Viton and Fluorel. Frequently used plastics are the semicrystalline
types, such as polytetrafluoroethylene (PTFE Teflon), fluorinated ethylene propyl-
ene (FEP Teflon), and polychlorotrifluoroethylene (PCTFE, Kel-F 81), and amor-
phous polymers such as polyimides (Vespel SP21).4
Table 9.5 shows minimum ignition temperatures for selected plastics and
elastomers,3 and Table 9.6 shows similar data for lubricants, adhesives, and fabrics. 3
Table 9.7 gives combustion rates for selected nonmetals. 3

Table 9.5. Minimum Ignition Temperature of Selected Plastics and


Elastomers in Oxygen at 1 atm Pressurea

Material Minimum ignition temperature (K)


Polyimide (Vespel) 773
Chlorotrifluoroethylene (CTFE) 773
Tetrafluoroethylene (TFE) 773
Duroid 5600 741
Duroid 5813 736
Duroid 5870 725
Duroid 5650 717
Rulon A 736
RulonB 733
RulonC 731
Graphite asbestos 733
Polymethyl methacrylate (Plexiglas) 703
TFE (carbon-filled) 693
Fluorinated ethylene propylene copolymer (FEP) 685
Silicone rubber 663
Kel-F 5500 613--625
Kel-F 3700 605-614
Carbon 603
Fluorosilicone 593
Polyvinyl chloride 663
Nylonb 618
Mylarb 593
Butyl rubberb 548
Neopreneb 523--543
Polyethylene b 433-493
Natural rubberb 423

a Ref. 3.
b Not recommended for oxygen service; included for comparison only.
Oxygen Hazards 127

Table 9.6. Minimum Ignition Temperature of Selected


Lubricants, Adhesives, and Fabrics in Oxygen at 1 atm
Pressurea

Minimum ignition
Material temperature (K)
Lubricants
Tetrafluoroethylene (TFE) lubricant 778
Chlorotrifluoroethylene (CTFE) grease 773
Halocarbon grease 25-10 704
Halocarbon oil 13-21 700
Oxyweld64 683
Silicone grease 643
Adhesives
Fused TFE 738
Oxyseal (2) 620--633
Epoxy (Armstrong A-6) 583
Fabrics
Nomex 763
Orion 703
Nylon 633
Dacron 583-663

a Ref. 3.

Table 9.7. Combustion Rate of Selected Nonmetals in Oxygena

Combustion rate (cmls) in exposure of:

Material 21% Oz, I atm 100% 0z, 0.2 atm 100% 0z, I Atm
Cotton 6.35 2.54 18.8
Dacron 1.78 2.29 5.84
Epoxy 0.30
Neoprene 0.25 1.02
Nomex 1.32 0.79 2.44
Nylon (fabric) 0.81 1.17 2.59
Polyethylene 0.15 0.69
Polyvinyl chloride 0.76 2.54
Polyurethane 1.42 1.78
Silicone 0.51 2.79
Velcro 0.61 1.22

a Ref. 3.
128 Chapter 9

9.4. CLEANING FOR OXYGEN SERVICE

Effective cleaning will eliminate loose scale, rust, dirt, weld splatter and
welding flux, particles, films, greases, oils, and other unwanted matter. Equipment
intended for use in oxygen systems must be cleaned of all foreign substances, both
to eliminate the possibility of unwanted reaction with the oxygen and to prevent
contamination of the oxygen that could render it hazardous or useless for its later
use. Before being placed in service, any equipment that might come into contact
with gaseous or liquid oxygen must be cleaned according to established proce-
dures. 8 Such items include liquid or gas storage vessels, either stationary or for
transport, heat exchangers, piping, fittings, valves, pressure regulators, and instru-
mentation. All contaminants that could cause malfunctions, fires, or explosions
must be completely removed. Films of grease, oil, or other organic materials
(including fingerprints) must be eliminated. Particles that could cause clogging of
flow passages, such as scale, rust, dirt, weld spatter, or welding flux, must be
removed. Also, none of the cleaning agents should remain after the cleaning process
is complete, and precautions must be taken to ensure that no recontamination can
occur before the item is placed in service.
Whenever possible, all items should be disassembled for cleaning ifthere is a
possibility of either a contaminant or one of the cleaning agents remaining in the
system in dead ends or other difficult-to-reach places. The method of cleaning must
be established beforehand to assure that all piping dead ends and branches are
properly cleaned. Methods of testing for satisfactory cleanliness must be estab-
lished beforehand. No one cleaning procedure can be satisfactory for all situations.
The proper cleaning procedure will depend upon the type of contaminant, the
location and degree of contamination, the geometry of the piece to be cleaned, and
the base material of the part to be cleaned. A typical cleaning procedure might
include such steps as mechanical cleaning (brushing or gas blasting), steam clean-
ing or cleaning with hot water and detergent, alkaline (caustic) cleaning, acid
cleaning, solvent washing (including ultrasonic), vapor degreasing, rinsing, drying,
and purging. 8 In all cases, the process selected must be compatible with the material
being cleaned and the contaminant being removed.
Precleaning is intended to remove gross amounts of foreign material such as
scale, dirt, solid objects, and hydrocarbons. Removal may be accomplished by such
processes as sweeping, vacuuming, swabbing, blast cleaning, wire brushing, or
grinding.
Steam or hot-water cleaning is usually assisted by the addition of detergents
to remove dirt, oil, and loose scale. Most detergents are water-soluble and are best
removed by flushing with clean water. The system can then be dried by purging
with dry, oil-free air or nitrogen gas.
Caustic or alkaline cleaning can be performed by spraying, immersion, flush-
ing, or hand swabbing. The cleaning solution should be warm to hot [37.8-82.2 C
Oxygen Hazards 129

(100-180 OF)]. Cleaning agents should be chosen that do not react chemically with
the materials being cleaned. The effectiveness of the rinsing process can be
determined by testing the exiting rinse water to see when the pH of the effluent
equals that of the incoming water. The system can then be dried as above. 8
Acid cleaning is performed by immersing the object to be cleaned in a suitable
acid solution, usually at room temperature. Large areas can be flushed with a stream.
Phosphoric acid-based cleaning agents can be used with any metal. Hydrochloric
acid-based cleaning agents are recommended only for carbon steels and low-alloy
steels. These agents will remove rust, scale, and oxide coatings, and they will also
strip chromium, zinc, or cadmium platings. Hydrochloric acid should not be used
on stainless steel because it might cause stress corrosion. Chromic acid- and nitric
acid-based cleaning agents are recommended for aluminum, copper, and their
alloys. As before, the cleaning process must be followed by rinsing and drying. 8
Solvent washing is used to remove organic contaminants. Cleaning may be
done by recirculation of the solvent in a closed system or in an ultrasonic cleaner.
Upon completion of the cleaning process, the solvent may be removed by draining
and purging with dry, oil-free air or nitrogen. The purge gas should be recirculated
until all traces of the solvent are removed. A halogen leak detector may be used
with chlorinated solvents to detect any remaining solvent. The test method should
be agreed upon by the manufacturer of the equipment and the purchaser. 8
Vapor degreasing is the removal of soluble organic materials by the washing
action of solvent vapors condensing upon the surface of the equipment to be
cleaned. Typical solvents used in this process include methylene chloride, trichlo-
rofluoroethane, perchloroethylene, trichloroethane (methyl chloroform), and
trichloroethylene. All of these solvents require special safety precautions. The
appropriate Material Safety Data Sheet should be obtained from the solvent
manufacturer. It should be read and all precautions observed and in place before
any use of the solvent is undertaken. Concerns are with toxicity and combustibility.
Also, proper disposal procedures for spent cleaning solution must be followed.
Solvent removal is as indicated above for solvent washing. Carbon tetrachloride
must not be used in any cleaning process. 8
After cleaning, several inspection techniques can be used to detect residual
contaminants. Visual inspection can be made with either white or ultraviolet light
(which depends upon the ability of many organic substances to fluoresce). A wipe
test with clean white paper or a lint-free cloth can be used to detect contaminants
in areas that are not visually accessible. The area should not be rubbed sufficiently
hard to remove an oxide film, which could be confused with actual surface
contamination. The paper or cloth can then be examined under an ultraviolet light.
Oily residues can be detected by a "water break test," in which the surface is wetted
by clean water. Ifthe water shows droplets or beads, this indicates the presence of
organic contamination that must be cleaned. A solvent extraction method depends
upon the ability of the solvent to dissolve an organic contaminant. This test cannot
130 Chapter 9

be used in a system that contains components that could be attacked by the solvent. 8
In any cleaning process, the use of heat should be carried out with caution where
parts to be cleaned contain materials that might be damaged by excess heat. An
example would be parts that contain multilayer thermal insulation.
Although the permissible level of contamination will depend upon the actual
application, a typical acceptable level for particular contaminants in oxygen service
has been given8 as 500 mg/m2 . Once a satisfactory level of cleanliness has been
attained, the part should be packaged to prevent the subsequent introduction of
impurities. The cleaned part should also be labeled as having been cleaned for
oxygen service. Cleaning methods described above involve chemicals that may
require special handling and disposal procedures. Additional details may be found
in Refs. 3,4, 7, and 8.

9.5. OPERATIONAL PRECAUTIONS

Most oxygen system malfunctions are caused by incompatibility of materials,


structural failures, or contamination. 3 Safe operation with an oxygen system
requires that safety be considered in every phase of plant design, construction, and
operation. Personnel that will operate or design oxygen systems must be familiar
with oxygen's physical, chemical, and hazardous properties. They must know the
cleanliness requirements of the system, the compatibility of materials utilized, how
to recognize system limitations, and how to respond to any failure that could occur.
Safe interfaces should be maintained so that no single failure could lead to an
accident. System design should promote leak prevention, adequate ventilation, and
elimination of ignition sources. Any failures of support systems, such as electric
power, should result in a fail-safe shutdown of the system. Flows should be limited
to subsonic velocities. A hazards analysis should be performed to identify condi-
tions that could cause serious accidents.

9.6. AIR CONDENSATION

Because oxygen condenses to a liquid at 1 atm pressure and 90 K, surfaces


below this temperature can condense oxygen. Cryogens such as liquid nitrogen and
the colder liquid cryogens like neon, hydrogen, and helium can also condense air.
If vent pipes or tubes transferring these colder cryogens are exposed to the
atmosphere, significant quantities of air can be condensed on them. The condensed
air can cause cold embrittlement problems if allowed to fall on materials that are
sensitive to cold embrittlement, such as carbon steel. Furthermore, as discussed in
Chapter 6, the condensed air will not have the same composition as the surrounding
atmosphere. Rather, the constituent having the higher boiling point will be enriched
in the condensate. Figure 6.1 shows the phase equilibrium diagram for the conden-
Oxygen Hazards 131

sation of air. Furthermore, if the "liquid air" condensed in this fashion is allowed
to accumulate and then to evaporate, during the evaporation process further oxygen
enrichment can take place.
The condensation of air by liquid-nitrogen can also occur if a liquid-nitrogen
surface is exposed to the atmosphere. This process leads to a contamination of the
liquid nitrogen, and if the nitrogen is subjected to nuclear radiation-for example,
if the nitrogen is used to cool an experiment in a nuclear reactor--the nuclear
radiation flux can produce ozonides or nitrogen oxides within the liquid nitrogen.
These compounds are explosive upon warming to room temperature. On a number
of occasions, explosions have occurred in liquid-nitrogen Dewars that were warm-
ing up to room temperature after having been left open to the atmosphere while in
the radiation flux of a nuclear reactor. The explosive compounds have been
observed to have a greenish-yellow color and were located on the walls of the
containment vessel near the surface of the liquid nitrogen. Advisable precautions
include starting with pure liquid nitrogen (oxygen content below 10 ppm), trans-
ferring liquid nitrogen in closed systems, and keeping the cryostat closed and under
a positive pressure with respect to the external atmosphere. If liquid nitrogen
boil-off is repeatedly replenished, greater amounts of ozone or ozonides can be
accumulated, constituting a greater hazard. Such a concentration effect can be
prevented by providing a liquid drain and a continuous supply flow of the liquid
nitrogen or by allowing the cryostat to become completely empty and warmed to
ambient temperature before refilling. 9

9.7. OZONE

Liquid ozone (0 3 ) is an unstable, dark blue liquid with an NBP temperature


of 161 K (-112C) and a melting point temperature of 80 K (-193C). As
mentioned in Chapter 2, it is highly toxic. In addition, it can decompose explosively
when shocked or exposed to heat or flame or by chemical reaction with reducing
agents. IO Pure 100% liquid ozone can be kept at 90 K (cooled by liquid oxygen).
However, the smallest provocation, such as a spark, fast warming, or warming to
the NBP temperature, can cause detonation. 11

REFERENCES

I. Timmerhaus, K. D., and Flynn, T. M. (1978). Safety with cryogenic systems, in Advances in
Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 23, pp. 721-729, Plenum Press, New York.
2. Compressed Gas Association (1982). Accident Prevention in Oxygen-Rich and Oxygen-Deficient
Atmospheres, CGA Pamphlet CGA P-14, Arlington, Virginia.
3. Schmidt, H. w., and Forney, D. E. (1975). ASRDI Oxygen Technology Survey, Vol. IX: Oxygen
Systems Engineering Review, NASA Report SP-3090, National Technical Information Service,
Springfield, Virginia.
132 Chapter 9

4. National Aeronautics and Space Administration (1995). Safety Standard for Oxygen and Oxygen
Systems, Guideline for Oxygen System Design, Material Selection, Operation, Storage, and
Transportation, NASA Report NSS-1740.15, Office of Safety and Mission Assurance, Washing-
ton, DC.
5. Lucas, W. R., and Riehl, W. A. (1960). An Instrument for the Determination ofImpact Sensitivity
of Materials in Contact with Liquid Oxygen, ASTM Bulletin No. 244, American Society for
Testing and Materials, Philadelphia, Pennsylvania, pp. 29-34.
6. Key, C. F. (1972). Compatibility of Materials with Liquid Oxygen-Vol. I, National Aeronautics
and Space Administration Technical Memorandum NASA TM X-64711, George C. Marshall
Space Flight Center, Alabama.
7. Hord, J. (1971). Safety with cryogenic oxygen and nitrogen systems, in Technical Manual of
Oxygen/Nitrogen Cryogenic Systems (A. F. Schmidt, ed.), Chap. 4, U.S. Air Force Report NAVAIR
06-30-501, U.S. Air Force.
8. Compressed Gas Association (I985). Cleaning Equipment for Oxygen Service, CGA Pamphlet
G-4.1, Arlington, Virginia.
9. Gault, J. D., Logan, K. w., and Danner, H. R. (1973). Ozone formation by the radiolysis ofliquid
nitrogen: Calculation and measurement, Nucl. Safety 14 (September-October), 446.
10. Sax, N. Irving (I 984). Dangerous Properties ofIndustrial Materials, Van Nostrand Reinhold, New
York.
II. Kaye, S. M. (1978). Encyclopedia ofExplosives and Related Items, Vol. 8, U.S. Army Armament
Research and Development Command, Dover, New Jersey.
Chapter 10

Slush Hydrogen

Although slush hydrogen has been studied for about three decades, its use on a
larger scale has become of greater interest because of its importance to aerospace
applications such as the National Aero-Space Plane (NASP). This chapter discusses
briefly the properties and characteristics of slush hydrogen that can influence the
safety of its handling, the nature of potential safety hazards arising from these
properties, and the design and operational considerations needed to make safe the
operation of slush-hydrogen systems. 1 In some cases, the safe handling of slush
hydrogen will require the further elucidation of some safety problems. A discussion
of safety problems that need further research, either analytic or experimental, or
both, is given in Chapter 12.

10.1. ADVANTAGES OF SLUSH HYDROGEN

For the use of hydrogen as a fuel, slush hydrogen offers two advantages over
liquid hydrogen. First, slush hydrogen has a greater density than liquid hydrogen,
the low density of which is a disadvantage when large quantities of hydrogen are
to be transported, especially in aerospace applications. The density of slush hydro-
gen that is 50% solid by mass is 15% greater than that ofliquid hydrogen at its NBP
(see Table 10.1). Second, if the refrigeration available in the cold hydrogen is to be
used for a cooling function, slush hydrogen (50% solid by mass) affords an
additional 18% refrigeration capacity compared to that available from the evapo-
ration of liquid hydrogen at its normal boiling point.
Both of these advantages are of great importance in aerospace applications.
The increased density of slush hydrogen affords the possibility of decreasing the
tankage-to-fuel mass ratio, thus enhancing the payload capacity. The increased
cooling capacity of slush hydrogen becomes more important as the velocity of the
vehicle within the atmosphere is increased.
133
134 Chapter 10

Table 10.1. Pertinent Hydrogen Propertiesa

Temperature Vapor pressure Density Increase in


Stateb (K) {kPa [psi] (absolute)} [kg/m3 (lb/ft3)] density" (%)
Liquid hydrogen (NBP) 20.27 \01.33 (14.7) 70.79 (4.42)
Liquid hydrogen (TP) 13.80 7.04 (\.02) 77.04 (4.81) 8.8
Slush (50% solid by mass) 13.80 7.04 (\.02) 8\.50 (5.09) 15.1
Slush (50% solid by volume) 13.80 7.04 (\.02) 81.77 (5.11) 15.1
Solid hydrogen 13.80 7.04 (\.02) 86.50 (5.40) 22.2

a Ref. I.
b Abbreviations: NBP, normal boiling point; TP, triple point.
C Relative to liquid hydrogen at NBP.

Melting Line

SOUD UQUID

~
~
!!? Liquid Vapor
a..
Pressure CP

VAPOR

Temperature

Fig. 10.1. General phase diagram (pressure vs. temperature). 2 TP and CP represent the triple point and
the critical point, respectively.
Slush Hydrogen 135

10.2. PROPERTIES OF SLUSH HYDROGEN

Several of the physical properties of slush hydrogen can influence the safety
of operation of one or more of the systems necessary for its use. These systems
include those for production, transfer, transport, storage, and upgrading or replen-
ishment of the solid fraction. The properties considered in the following sections
are those that are of the greatest interest in discussing the safety implications of
handling slush hydrogen.

10.2.1. Equation-or-State Relationships


If the pressure in the vapor space of a container of liquid hydrogen is lowered
by pumping off the vapors, the boiling-point temperature of the liquid also de-
creases until the triple point (TP) is reached. At this point {for hydrogen, pressure
of7.04 kPa [1 psi] (absolute) and temperature of 13.80 K} it is possible to have all
three phases-gas, liquid, and solid-in equilibrium. The average density of the

Solid
Solid and
Liquid

Liquid and Vapor

1
Solid and Vapor

Fig. 10.2. General phase diagram (temperature vs. entropy)? Point I represents 100% solid, point 2 the
triple point, and point 3 saturated vapor at the triple-point temperature.
136 Chapter 10

mixture within the container will then depend upon the relative proportions of each
of the three phases.
Two properties of slush hydrogen that obviously could contribute to the
existence of safety hazards are the lower vapor pressure (subatmospheric) at the TP
and the greater density, which monotonically increases as the temperature ofliquid
hydrogen is lowered from the NBP of equilibrium hydrogen (20.27 K) to the TP
(13.80 K) and further increases upon freezing. These density increases upon cooling
and freezing imply a correspondingly significant increase in volume that the
containment system must accommodate upon melting of the solid phase and/or
warming of the liquid phase above the slush temperature. Table 10.1 summarizes
values of these properties. Values are included for 50% solid-liquid mixtures both
by mass and by volume to illustrate the small, but finite, difference between these
two quantities.

200

N~P

V
100

/
V
/
/
V
I
10

TP

5
13 15 17 19 21
Temperature (I<)

Fig. 10.3. Vapor pressure of parahydrogen vs. temperature, from the triple point (TP) to the normal
boiling point (NBp). 3
Slush Hydrogen 137

Figure 10.1 gives a qualitative view of a phase diagram of a generic substance


in a plot of pressure versus temperature. 2 Figure 10.2 is a similar plot oftemperature
versus entropy. 2

10.2.2. Vapor Pressure


Figure 10.3 shows the vapor pressure ofliquid parahydrogen between the TP
and the NBP. Figure lO.4 is similar to Fig. lO.3 except that it covers the range from
the NBP to the critical point (CP).3 The low vapor pressure at temperatures below
the NBP indicates the degree to which the total system pressure can fall below that
of the local atmosphere as the temperature is decreased below the NBP.

1~'-------------r------------.-------------.-----'

1~~------------~------------~---------7L-~----~

"iii"
a. ~
C
!
~
!
a.

!
200

l00~~~-.--~~--~--~-r--+-~--~--~-+--~~
20 22 24 26 28 30 32 34
Temperature (I<)

Fig. 10.4. Vapor pressure of parahydrogen vs. temperature, from the normal boiling point (NBP) to the
critical point (CP).
138 Chapter 10

10.2.3. Melting Curve


Figure 10.5 presents the melting curve (melting pressure as a function of
temperature) for parahydrogen from the TP to 50 K. Figure 10.6 shows a similar
plot over the lower temperature range from the triple-point pressure to the critical-
point pressure. 3 An examination of Figs. 10.1-10.6 indicates that, except at the TP,
it is necessary to maintain a total system pressure greater than the vapor pressure
in order to maintain a two-phase solid--liquid mixture. This elevated pressure can
be achieved by introducing a noncondensable, second component (helium gas), by
having only solid and liquid present, or by establishing temperature stratification
in the liquid layer that may exist above the liquid-solid mixture. The relatively low
thermal conductivity of liquid hydrogen can allow a temperature gradient to be

500

100 ~
v----
V
V

/
/
10

1
10 15 20 25 30 35 40 45 50
Temperature (K)

Fig. 10.5. Melting pressure for parahydrogen vs. temperature, above the triple point (TP).3
Slush Hydrogen 139

1.4

I Crt,~ Po" "'...."

V
1.2

1.0

~0.8 /
~
~
~
~ 0.6
a.

0.4
V

L;mp"~,,
0.2

0.0
13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5
Temperature (K)

Fig. 10.6. Melting pressure for parahydrogen vs. temperature, from the triple-point pressure to the
critical-point pressure. 3

maintained in the liquid layer so that the upper surface of the liquid layer can remain
at a temperature at which its vapor pressure is higher than that of the slush-hydrogen
region.

10.2.4. Heat of Transition


Table 10.2 summarizes some heats of transition for various phase changes of
parahydrogen. Note that the heat of phase change from solid hydrogen to liquid is
almost an order of magnitude less than the heat of vaporization of liquid hydrogen
at the NBP. This fact can complicate the problem of storage of slush hydrogen, and
higher replenishment rates may be required in some cases as a result. Table 10.2
also gives the heat of vaporization of liquid helium for comparison.
140 Chapter 10

Table 10.2. Heats of Transition for ParahydrogenO

Heat of transitionC
Phase changeb [Jig (Btullb)]
Solid-liquid (TP) 58.23 (25.03)
Solid-vapor (TP) 507.39 (218.1)
Liquid-vapor (TP) 449.16 (193.1)
Liquid-vapor (NBP) 445.59 (191.6)
Helium, liquid-gas (NBP)d 20.3 (8.7)

a Ref. 1.
b Abbreviations: TP, triple point; NBP. nonnal boiling point.
C Additional data on the thennodynamic properties ofparahydrogen
in the temperature range from I K to 22 K are given by Mullins
eta/. 4
d Included for comparison purposes.

3X10 19

/
V
E
u
2X10 19
g
f
'til

/
'i
II:

~
&i
iii

V
1X10 19

/
o
o 20 40 60 80
Voltage (V)

Fig. 10.7. Electrical resistivity of liquid parahydrogen vs. applied voltage. s


Slush Hydrogen 141

10.2.5. Electrical Conductivity


The electrical conductivity ofliquid hydrogen has been measured by Willis,5
who found typical resistivities in the vicinity of 10 19 ncm. However, the data
reproduced in Fig. 10.7 show the resistivity to be a linear function of applied
voltage. As Willis pointed out, this is an indication that it is not strictly correct to
consider the electrical conductivity of liquid hydrogen in terms of Ohm's law.
Although a current can be passed through the liquid hydrogen, this current can be
explained in terms of charge carriers formed by background radiation. Thus, the
current-carrying capacity is more or less independent of the imposed voltage.
However, the low capability to carry an electrical current can make it difficult for
any accumulated electric charge to dissipate, and if flowing slush hydrogen can
generate static electricity, sufficiently large charges could accumulate to cause an
ignition of an unwanted mixture of hydrogen with air.

10.2.6. Equilibrium between Orthohydrogen and Parahydrogen


A property of hydrogen that can influence a number of its other properties,
such as specific heat and thermal conductivity, is the existence of the two forms of
hydrogen, orthohydrogen and parahydrogen-the difference being in the orienta-
tion (parallel or antiparallel) of the spins of the nuclei in the hydrogen molecule.
The parahydrogen form is in a lower energy level; however, the relative proportion
of the two forms in hydrogen in thermal equilibrium is a function of temperature
as shown in Fig. 10.8. 3
As the temperature of hydrogen is lowered, the orthohydrogen will convert to
parahydrogen. Ifuncatalyzed, this conversion is slow but occurs at a finite rate, and
the conversion is accompanied by a release of heat, which, at 20 K, is comparable
to the heat of vaporization. [At 20 K the heat of conversion of orthohydrogen to
parahydrogen is 703 JIg compared to 446 Jig for the heat of vaporization ofNBP
liquid hydrogen. The heat of conversion is sometimes reported3 as the heat of
conversion of normal hydrogen (75% orthohydrogen) to parahydrogen, which is
525 Jig.] If the rate of decrease of orthohydrogen concentration is expressed as
(-dxldt), the bimolecular reaction can be described by

(-dx/dt) = kx;2
where x is the concentration of orthohydrogen and k is the rate constant,6 with k
having been determined to be equal to 0.01l4/h.7 The spontaneous conversion of
orthohydrogen to parahydrogen continues even in the solid state, where the con-
version rate may be even greater than it is in the liquid. 8
The conversion rate is sufficiently slow that if normal ambient-temperature
hydrogen is liquefied, the resulting liquid is of approximately the same composition
as the initial ambient-temperature gas (75% orthohydrogen) and will have an
increased evaporation rate because of the heat release by the slow conversion to
142 Chapter 10

100

80

c:
Q)

~
-g,
;
.t::

a. 60
'E
~Q)
a.

40

~
20
o 100 200 300
Temperature (K)

Fig. 10.8. Equilibrium percentage ofparahydrogen VS. temperature. 3

parahydrogen. (About 50% will be lost in a week.) Thus, for efficient storage,
commercial liquid hydrogen is converted to the parahydrogen form during the
liquefaction process. A parahydrogen concentration of at least 95% is usually
guaranteed by commercial liquid-hydrogen suppliers, although this value can be
higher in the delivered product. The equilibrium mixture of the two forms of
hydrogen at 20.3 K is 99.8% parahydrogen.

10.2.7. Solubility of Helium in Liquid or Slush Hydrogen


The solubility of helium gas in liquid hydrogen is a function ofthe temperature
as well as of the pressure of helium in the gas phase in equilibrium with the liquid
phase. Although the solubility of helium in slush hydrogen has not been determined,
several experimenters have investigated the solubility of helium in liquid hydrogen
over a range of temperature and pressure.9-11 Some of the results are reproduced in
Fig. 10.9.
Slush Hydrogen 143

15.5 K 17.07 20.4 23 26

1.5~--------+-~+-------~--+-------~~~~~------~

0.5+---F-hH---+-----------+-------------l------------1

O~~~--~~-+~--~~~~--~~~~--~~~~--~
o 2 3 4
Percent Helium in Liquid Hydrogen (mol%)

Fig. 10.9. Liquid portion of the phase diagram of the hydrogen-helium system, showing the solubility
of helium in the hydrogen liquid phase. II
144 Chapter 10

10.3. POTENTIAL SAFETY HAZARDS OF SLUSH HYDROGEN

In general, the hazards of concern in the handling of slush hydrogen must


include the hazards arising in the handling of gaseous hydrogen and those arising
in the handling of liquid hydrogen, in addition to those arising from the slush
hydrogen itself. In varying degrees, any of the properties of slush hydrogen
discussed in Section 10.2 can give rise to, or at least exacerbate, safety problems
in its production or handling.

10.3.1. System Pressure Variability


Because the vapor pressure ofthe hydrogen at a temperature of 13.8 K is only
7.04 kPa [1 psi (absolute)], there is always a concern that the total pressure in a
system containing slush hydrogen will fall below that of the local atmosphere. This
potentially negative gauge pressure could occur accidentally, or it could be part of
a planned production process.
In the case of stationary storage, the storage vessels can be properly designed
to withstand the potentially damaging negative pressures with respect to the
external atmosphere. Flight or other lightweight tankage, on the other hand, usually
cannot tolerate a negative gauge pressure.
In addition to concerns about structural damage arising from internal pressures
that are negative with respect to the external atmosphere, if such a condition, either
planned or inadvertent, can occur, precautions must be taken to prevent the intrusion
of atmospheric air into the storage space. Entering air will condense and, in so
doing, will cause additional melting of the solid fraction of the slush, but at 13.8 K
the condensed air will exhibit essentially zero vapor pressure, thus making its
detection difficult. In the case of slush-hydrogen production facilities, the use of
the freeze-thaw method of production (see Section 10.4.2) requires the existence
of negative gauge pressures.
As can be seen from Fig. 10.1, as long as thermal equilibrium is established
within a single-component system, the three phases can only exist at the TP {7.04
kPa [1 psi (absolute)]). However, there are several methods of storing slush
hydrogen at or above normal atmospheric pressure. The simplest method (in
principle, but not in practice) would be to have a system of only two phases, liquid
and solid. The continuous in-leakage of heat plus the large expansion upon the
melting of the solid make this expedient difficult to apply; however, it would be
possible to do so with dual-wall inner tanks with bellows construction in the
innermost (slush) container.
Another method of storing and handling slush hydrogen at a pressure approxi-
mately equal to the external atmosphere is that of allowing a thermal gradient in a
liquid-hydrogen layer above the slush so that the surface temperature is at 20.27 K.
In this manner, the surface of the liquid will have a vapor pressure of 101.325 kPa
(I atm), or higher if the temperature is allowed to rise above 20.27 K. Obviously,
Slush Hydrogen 145

this method cannot be used if, either intentionally or unavoidably, stirring or


agitation of the storage vessel's contents can occur and destroy the thennal
stratification. Ifthis method is used, care must be taken to see that the total mixture
is not sufficiently agitated to destroy, or even partially destroy, the thennal gradient
within the stored mixture. If that were to occur, some of the solid hydrogen would
melt and cool the supernatant liquid, lowering its vapor pressure and producing a
pressure in the interior of the system that is lower than that of the external
atmosphere. It is of interest to note that the vibration caused by road transport of
liquid hydrogen in trailer-mounted Dewars is sufficient to destroy thennal stratifi-
cation within the liquid hydrogen being transported 12 (see Section 5.1).
The pressure within the system can also be maintained at nearly nonnal
atmospheric pressure by the addition of helium gas, which is not condensable at
temperatures above 5.2 K. However, temperature stratification is also possible in
the gas space\3 (which contains mostly helium in this case). For a fixed quantity of
pressurization gas in the ullage space, an increase in thennal stratification will
increase pressure, and with decreasing stratification the pressure will decrease. The
distribution of heat input, flow rates, tank configuration, tank material, agitation,
motion-caused vibration, and changes in orientation with respect to the gravita-
tional field are all factors that can affect the thennal gradient. Also, gas and/or liquid
flow and the geometry of the vessel can cause mixing in the vapor phase and thus
influence the temperature gradient and consequently the quantity of helium pres-
surization gas required at any time. Therefore, it is necessary to have a complete
understanding of the processes that can either promote or destroy temperature
stratification, and to maintain an acceptable pressure would require a system to
control the inventory of helium in the ullage space.

10.3.2. Pressure Oscillations


An additional pressure control problem can arise from thermal acoustic
oscillations (TAO) that stem from the ingress of the slush mixture into a warmer
area (typically, a gauge line or instrumentation tube). 14,15 (See Section 5.4.2.)
TAO can result in periodic pressure excursions to greater than acceptable
values and can also result in an unacceptable heat input into the system. In a 500-L
(l32-gallon) slush-hydrogen storage Dewar, the addition of a single 6-mm-diameter
(l/4-in.-diameter) stainless-steel tube connecting the storage volume to ambient
temperature was found to increase the heat leak to the Dewar by a factor of 10 (from
0.5 W to 5 W). The same Dewar containing liquid hydrogen at the nonnal boiling
point experienced TAO with a frequency of3-5 Hz and pressure oscillations of3-5 Torr
(0.06-0.1 psi). When the Dewar contained slush hydrogen, the frequencies in-
creased to 5--10 Hz, and the pressure variation to 250 Torr (4.8 psi).
146 Chapter 10

10.3.3. Volume Expansion upon Melting and Warming


The density data of Table 10.1 show that a significant volume expansion occurs
upon the melting of the solid hydrogen and also upon the subsequent wanning of
the liquid to temperatures above the TP. For a mixture of 50% solid (by mass), the
total expansion to reach the density of liquid hydrogen at the NBP is about 15%.
All storage systems will have some heat input, thus requiring either continuous
slush replenishment or some provision to accommodate this expansion. This might
be done with the provision of sufficient ullage space to accommodate the expansion
caused by the heat input over the anticipated storage time, so that, as the mixture
absorbs heat, liquid or slush hydrogen would not have to be expelled from the
storage system. Even with a sufficiently large ullage space, it will still be necessary
to vent gas from the ullage space if the ullage pressure rises to the allowable upper
pressure limit for the storage system.

10.3.4. Electric Charge Buildup in Flowing Slush Hydrogen


Investigations concerned with the possibility of electric charge buildup in
flowing liquid hydrogen have resulted in the conclusion that this is not of great
concern in the flow of single-phase liquid hydrogen. 5,16 However, the presence of
solid particles within the flowing hydrogen was mentioned as a possible source of
increased electric charge buildup. This is a possible source of hazard about which
very little is known (see Section 12.4.6).

10.3.5. Aging Effects in Large Storage Quantities


Studies of the storage of slush hydrogen for periods of up to about one month
have demonstrated that storage over this period of time, in depths up to one meter,
should not have any adverse effect upon the subsequent handling characteristics of
the slush. I? However, large-scale use of slush hydrogen will involve considerably
greater depths and longer storage times. The possible effects upon the solid particle
size and critical flow velocities should be examined (see Section 12.4.7).

10.3.6. Conversion of Orthohydrogen to Parahydrogen


In large-scale storage of slush hydrogen, the heat generation caused by the
residual orthohydrogen-to-parahydrogen conversion at 95% parahydrogen is about
the same as the total heat leak into a well-insulated storage Dewar. Because the heat
of melting of the solid hydrogen, as shown in Table 10.2, is only about 58 Jig, the
additional heat input is worthy of consideration. The additional loss of solid
hydrogen could add to the replenishment flow quantities, which could in turn
compound existing safety problems.
Slush Hydrogen 147

10.3.7. Helium Effectiveness in Pressure Control


The quantity of helium required to maintain an acceptable pressure over the
slush surface will be affected both by any solubility of the helium in either the slush
or in a supernatant liquid layer and by temperature gradients within the helium gas
layer above the fluid surface. Factors that can influence the presence or absence of
such temperature gradients include gas flow rates and the geometry of the particular
vessel being used. Although the helium solubility in slush hydrogen at low pressures
appears to be very small,9-11 both it and the possibility of a changing thermal
gradient in the ullage space above the surface must be considered in the manage-
ment of the helium inventory.

10.4. PREVENTIVE MEASURES

In order to have the safest operation, it is necessary to have the safest possible
system and to operate it in the safest way. Wherever possible, it is desirable to
provide protection against safety hazards within the design of the system. This,
along with sufficient operator training and well thought-out procedures, can ensure
the safest operation.

10.4.1. System Design


From a cryogenic standpoint, the low temperature coupled with the low heat
of melting of the solid fraction makes the difficulty of handling slush hydrogen
closer to that of handling liquid helium than that of handling liquid hydrogen. The
temperature of slush hydrogen (13.80 K) is lower than that of liquid hydrogen
(20.27 K), and the heat of transition (melting of the solid) is 58.23 Jig as compared
to 445.6 Jig for vaporization of NBP liquid hydrogen. Thus, for slush hydrogen,
both of these properties are intermediate between those ofliquid hydrogen and those
of liquid helium (heat of vaporization at 1 atm and 4.2 K is 20.3 Jig). One
consequence may be that of economics with respect to the ease ofloss ofthe desired
phase of hydrogen. However, from a safety standpoint, another consequence may
be a need for a faster response to emergency situations. In addition, the potentially
higher loss rates mean that larger quantities may have to be vented or provisions
made for their expansion and that higher flow rates may be required for upgrading
or replenishing the slush hydrogen.
In addition to the safety provisions needed for systems handling liquid or
gaseous hydrogen, the handling of slush hydrogen involves other constraints. For
any hydrogen system, in order to avoid cross contamination, vent systems should
not be interconnected. For slush-hydrogen systems, the possibility of pressures
negative with respect to the external atmosphere leads to the requirement that
additional protection be provided at vent points. The discharge ports of relief valves
and rupture disks must be designed to prevent the back flow of air into the system,
148 Chapter 10

either subsequent to their operation or because of possible leakage during nonnal


operation.
In view of the above factors, it is necessary that systems for handling and
storage of slush hydrogen be built with the lowest possible heat input (highest
quality thennal insulation) and that thennal design considerations should be based
more closely on liquid-helium service than on the more traditional liquid-hydrogen
service.
There is evidence that slush hydrogen does not block or plug valve seats. 18
However, for the storage or transfer of slush hydrogen on a larger scale for longer
periods of time, care must be taken to ensure that the transfer of a liquid-solid
mixture will not allow any accumulation of solid particles that could cause such
blocking or plugging.
Other precautions that must be taken include expedients like guard volumes
around potential leakage points such as valve stems and instrumentation feed-
throughs. The guard volume could be either a monitored vacuum space or a volume
filled with helium gas at a pressure greater than that of the external atmosphere. It
would also be desirable, where appropriate, to orient valves with the seat side
toward the slush volume.

10.4.1.1. Welded Construction


In order to minimize potential leakage points, as a primary requirement each
system involved in the handling of slush hydrogen should be designed to make the
maximum use of welded construction. Demountable joints should only be used
where absolutely necessary.

10.4.1.2. Leak Detection


State-of-the-art leak detection techniques (mass spectrometer helium leak
detectors) are to be used in the fabrication of all equipment in which slush hydrogen
is to be handled. The leak detection should be perfonned at as close as possible to
actual use conditions and after thennal cycling from ambient temperature down to
at least the temperature of liquid nitrogen (77 K ).
After the equipment is placed into service, it then becomes necessary to
monitor continuously for the intrusion of air from the atmosphere. The process by
which the detection of air intrusion can be accomplished is a subject that requires
further research (see Section 12.4.1). The most obvious method would be the use
of samples taken from the storage fluid, warmed to room temperature, and subjected
to gas analysis. Typical analysis techniques would include mass spectrometry or
gas chromatography. However, the problem remains of detennining how repre-
sentative ofthe entire stored volume a given sample would be. Furthennore, in the
analysis of the sample it might be difficult to avoid fractionation and adsorption
Slush Hydrogen 149

errors. In situ analysis would be desirable, but the method of doing this will have
to be developed.

10.4.1.3. Guard Volumes


Instrumentation tubes, flanges, wire pass-throughs, and valve stem packings
compromise, to some extent, the integrity of the otherwise more robust and
impenetrable all-welded systems. The locations of these entries into the system
provide potential leak points where atmospheric air could enter the system when it
is below atmospheric pressure. This possibility gives rise to the need for some
additional protection at appropriate locations. One method is to make use of
external volumes at high vacuum surrounding the vulnerable portions of the system
at (or potentially at) subatmospheric pressure. In this case the vacuum in the guard
volume must be monitored and provided with an alarm to warn of the loss of
vacuum.
Another method of providing additional protection against air intrusion is with
the use of an exterior surrounding space also sealed from the atmosphere and
pressurized with helium gas at a pressure above that ofthe external atmosphere. In
order to assure the effectiveness of this method, the pressure of helium in this guard
volume must be maintained and monitored.
Vacuum pump systems and discharge points of pressure relief valves and
rupture disks deserve special attention. For vacuum pumps, precautions must be
taken so as to prevent the intrusion of air into the subatmospheric system that could
either be caused by leaks or result from power failures.

10.4.2. Production Techniques


To date, most of the production of slush hydrogen has been by the freeze-thaw
technique. 17 In this production method, a vacuum is pumped on the liquid-hydrogen
surface until, at a residual absolute pressure of about 50 Torr, a film of solid
hydrogen forms on the surface. The pressure is then allowed to rise just enough to
cause melting of the solid around the circumference of the surface, and the
remaining solid then sinks down through the liquid because of its greater density.
The pressure can then be lowered again, resulting in the formation of a second solid
layer. This process can be repeated progressively, thereby increasing the fraction
of solid hydrogen that is produced.
A second production method uses an auger l9 ,20 cooled with cold helium. In
this method the auger is within a hollow cylinder that is cooled on its inside surface
with cold helium, either liquid or gas, flowing through the annular interior of the
cylinder. Because the entire apparatus is placed below the liquid-hydrogen surface,
hydrogen freezes on the inner surface of the hollow cylinder and is scraped offby
the rotating auger.
150 Chapter 10

Other possible production methods include magnetic refrigeration, the bub-


bling of cold helium through a liquid-hydrogen bath, and the Joule-Thomson (J-T)
expansion of a cold helium-bydrogen mixture. 21 The nature of the freeze-thaw and
the helium bubbling production methods calls for continuous operation close to the
TP pressure of approximately 1 psi (absolute). Although the auger method, and
possibly the J-T expansion production method, can be operated at or above
atmospheric pressure, safety precautions must take into account the possibility of
subatmospheric pressure conditions occurring.
Another item that deserves attention is the purity of the liquid hydrogen to be
used in the production of slush hydrogen. Specifications for liquid hydrogen call
for a purity of at least 99.995% (by volume) of hydrogen with a concentration of
parahydrogen of at least 95%. Total impurities may not exceed 50 ppm (by volume).
The combined concentrations of nitrogen, volatile hydrocarbons, and moisture may
not exceed 9.0 ppm. Oxygen plus argon are limited to 1.0 ppm, carbon monoxide
plus carbon dioxide to 1.0 ppm, and helium to 39 ppm?2,23 While the possibility
for concentration of impurities exists for any slush production method, especially
if upgrading is later required, the freeze-thaw method presents an obvious mecha-
nism for this to occur. Depending upon the length of storage time required and the
degree of replenishment or upgrading needed, it might be necessary to reconsider
the purity requirement of the liquid-hydrogen supply.

10.4.3. Materials Selection


From a structural standpoint, the proper selection of materials for slush-hydro-
gen service can be assured by making use of materials that have already been shown
to be suitable for liquid-hydrogen service. Such materials include a number of
aluminum alloys, austenitic stainless steels, brass, and copper. However, these
materials present a wide range of thermal conductivities, which can, in tum,
influence the existence of thermal gradients in the slush hydrogen during storage.
The desirability of maintaining thermal gradients, thus implying an acceptable
thermal conductivity of appropriate structural materials, must be considered along
with the strength-to-weight ratios, thermal expansion coefficients, and low-tem-
perature ductilities.
Although the temperature difference between slush hydrogen and liquid
hydrogen should not cause any problems in using materials suitable for liquid-hy-
drogen service, there remains the possibility that the solid particles flowing in the
slush could, over time, cause erosion of softer materials such as a valve seat. This
phenomenon, if it occurs, could result in leakage through the valve seat.

10.4.4. Storage, Aging, and Upgrading


Long-term storage of slush hydrogen may require upgrading or replenishing
of the solid fraction of the slush. With slush hydrogen, 50% solid by mass, the solid
Slush Hydrogen 151

fraction can be expected to decrease at the rate of about 0.5% per day in a well-built
storage Dewar. This decrease will be caused by the heat leak into the Dewar and
the residual orthohydrogen-to-parahydrogen conversion taking place spontane-
ously in the stored fluid. To preclude this decrease in solid fraction and! or to upgrade
the solid fraction above the level at which it was transferred into the storage Dewar,
a replenishment or upgrading process is desirable.

10.4.5. Pressure Control


There are two methods that appear practical for maintaining pressures at or
slightly above local atmospheric pressure. These methods involve either depend-
ence upon thermal stratification in a supernatant liquid-hydrogen layer above the
surface of the solid slush particles or the addition of a second, noncondensable
component, helium gas.
The use of a thermally stratified liquid layer can, in principle, enable the
maintenance of tank pressure at any pressure between the vapor pressures at the TP
and the CPo By venting at a controlled pressure, the temperature ofthe liquid surface
will stay in equilibrium with the desired pressure. A disadvantage to this method
of pressure control is that there are several processes that can act to destroy or at
least diminish the thermal stratification. Such mechanisms include vibration or
agitation of the containment vessel, any agitation of the fluid caused by the
withdrawal or addition of liquid or slush, or the addition of gas to the ullage space
in the Dewar. The effect of a change of orientation with respect to the gravity vector
(slosh) is not known, but such a change could also have a deleterious effect upon
maintaining a desired level of thermal stratification.
Although there has been some experience with thermal stratification in large
liquid-hydrogen Dewars,13 it is worth noting that the technique of allowing a
desirable level ofthermal stratification to occur in the liquid above slush hydrogen
is based on experimental evidence generated, in large part, in storage vessels made
of glass or stainless steel. In a storage vessel of this type, thermal stratification can
be maintained because the liquid hydrogen, if undisturbed, is an excellent insulator,
and the walls of the vessel have very low thermal conductivity. For ground storage,
these results will still be applicable. However, for some applications, tank walls
fabricated of lighter materials such as aluminum will be desirable, and these will
present much higher thermal conductivity, which can decrease or even destroy
thermal gradients. Because the pressure in the storage system depends upon the
temperature of the vapor/liquid interface, the pressure control of the system will be
influenced by the thermal gradient in the tank wall. This effect of material selection
is used to advantage in the unvented transport ofliquid helium. 24 The same effect
may be a plus or a minus in the storage of slush hydrogen, but it must be considered
along with the design of the gas entrances when selecting hydrogen or helium as a
pressurant for flight tankage or other storage Dewars.
152 Chapter 10

The other method of pressure enhancement, by adding a noncondensable


component to the ullage space, can only be accomplished with helium gas. The
temperature of the entering helium is important, but the additional pressure of the
helium can be added to the vapor pressure of the hydrogen to achieve any desired
pressure within the storage space. A possible complication can arise in determining
the quantity of helium to be added. The only local source of refrigeration usually
present is the melting of the solid fraction of the slush. The melting of the solid
gives rise to a volume expansion (and some consequent pressure rise) and at the
same time creates a liquid layer above the surface that can undergo some thermal
stratification, thus contributing to an additional pressure rise within the storage
system.
Thermal stratification can also occur within the ullage space. This allows the
consideration of the use ofthis temperature gradient to reduce the quantity of helium
needed to supply the necessary pressure enhancement. However, any mechanism
that can reduce or destroy the thermal gradient in the ullage space can also cause a
lowering of the pressure in the storage system. This possibility, in addition to any
solubility ofthe helium gas in the slush hydrogen, can make it difficult to calculate
the quantity of helium needed at any time. Fortunately, the solubility of helium in
slush hydrogen appears to be very slight under the expected conditions ofuse.9--11
Even though efforts can be made to avoid storing and handling the slush
hydrogen at subatmospheric pressures, it must be remembered that the possibility
of pressure collapse is always present, and this condition is unfavorable from a
safety standpoint. Consequently, the system design must be such that every possible
precaution is taken to minimize unwanted pressure variations.

10.4.6. Fluid Quantity Measurements


Safe operation of a cryogenic system requires that the system operators have
an accurate, complete, and continuous knowledge of the amounts and locations of
the cryogenic fluids being stored and in use. In the determination of fluid inventory
of slush hydrogen, it is necessary to make measurements for a single-component,
two-phase system. Although it is not difficult to determine the volume of a system
by methods such as a liquid-level measurement, this does not determine the mass.
It is also possible to measure the level of the solid fraction when settling is allowed
to take place in the slush-hydrogen system. However, without a greater knowledge
of the degree of packing of the solid, the total mass stored will still not be known.
A direct determination of total mass is desirable and could be made by means of
nuclear radiation attenuation or other methods whereby the mass concentration of
a representative sample is measured and the resultant value is assumed to be
representative of the entire contents ofa tank.
Slush Hydrogen 153

10.4.7. Thermal Acoustic Oscillations


Investigations have shown that TAO are a source of periodically elevated
pressure l5 and can pump large quantities of energy into the main storage volume. 25
The design of slush-hydrogen systems with consideration of aspect ratios and surge
volumes can help to minimize TAO problems. The magnitude of these oscillations
will depend upon the geometric and thermal parameters of the storage system, and
they might easily reach an unacceptably high amplitude. Methods to damp TAO
consist of expedients such as the use of properly placed damping volumes 15 or the
selection of proper length-to-diameter ratios in the piping of the system. Total
system pressure might also have an effect. Studies performed by Gu and Timmer-
haus provide an understanding of TAO that can assist in the design of systems that
will avoid or minimize TAO.14 However, each volume to be protected against
excessive pressure oscillations must be considered individually.

10.4.8. Volume Expansion


There is a significant volume expansion in the melting of solid hydrogen and
also in warming TP liquid to NBP conditions. Consequently, whenever there is no
source of cryogenic refrigeration or slush replenishment, the inevitable heat leak
into the cryogenic system will produce a melting of the solid hydrogen and/or
warming of the liquid hydrogen, which will in turn cause either a need for venting
from the ullage space or a rise in pressure in the storage system if venting is not
possible. As can be seen from Table 10.1, ifthe storage system is to be isolated from
a cryogenic refrigerator or replenishment system until the solid has all melted and
the liquid warmed to 20.27 K, even if all the gas is vented, an ullage space of over
15% will be needed if venting of the liquid is to be avoided.
Another possibility is that the slush storage vessel could be built with a double
inner container (within the customary vacuum jacket), with the innermost vessel
being of a bellows design. In this manner, helium gas could be used in the outermost
portion of the inner tank to pressurize the slush container, which could conform to
the quantity of its contents. Use of this type of tank would involve the additional
complications of added weight and difficulty of construction but would also
minimize the problems of maintaining an acceptable operating pressure.

10.4.9. Operational Criteria


In many cases of complex systems, design provisions cannot, by themselves,
take care of all safety problems, especially those arising unexpectedly. Therefore,
the highest degree of safety will be achieved by incorporating all possible safety
provisions in the design ofthe system and then controlling the manner in which the
system is operated.
The enhancement of overall safety can be achieved by the establishment of
standard operating procedures (SOPs) that outline the operating philosophy. These
154 Chapter 10

SOPs must then be supplemented by checklists covering each phase of the opera-
tion, including contingency checklists prescribing the proper response to possible,
but unintended, situations that could occur during operation of the system. Obvi-
ously, the checklists must be written by those who not only are cognizant of good
safety practices but also have a detailed knowledge of the actual design of the
system and fully understand its operation. This means that the checklists should be
written by personnel at the operational site and will be site-specific. The input of
the operating engineers and technicians is valuable in the writing of these checklists,
both because of their intimate knowledge of the system and its responses as well
as because their participation will assist these same people in their training in the
safety of operation of the system.
In slush-hydrogen systems there is always the possibility of the existence of a
negative pressure with respect to the external atmosphere. F or this reason, a periodic
warming of the system to a temperature above 90 K is advisable. Such a procedure
will permit the detection of air intrusion by analysis of the residual gas and thus
indicate whether any additional purging is needed. Operational procedures should
always be planned to preclude air intrusion.

10.4.9.1. Transfer of Slush Hydrogen


In the use of slush hydrogen, the transfer of this fluid will be required for such
processes as upgrading, replenishment, loading, and off-loading from storage
vessels. The two methods for accomplishing transfer are by pressure and by
pumping, either of which will probably be required at one time or another.
Pressurized transfer can be performed where a supply of pressurization gas is
available. In order to perform this type of transfer, it is necessary to know the
quantity of pressurization gas (helium or possibly hydrogen) needed in the supply
vessel as well as the allowable flow rates of both the gas and the slush so as to
preserve any needed thermal stratification and to achieve critical slush velocities.
Although the pumped transfer of slush hydrogen has not been investigated as
much as has pressurized transfer, there is some experience with this process. In this
work the pump was run at flow rates up to 0.022 m 3/s (350 gpm) and developed
pressure increases up to 179 kPa (26 psi). With the short run time of 79 min, no
sign of pump wear was detected. 26 For long-term operation, erosion of pump
components could be a problem, and much longer run times are necessary to prove
that a particular pump could be used for long-term operation. The size and
orientation of nozzles are of importance, and, for practical operation, the drive and
the pump should be thermally separated to reduce the loss of solid content of the
slush that would be caused by the inefficiencies of the pump drive.
The transfer of slush hydrogen has been studied and pressure drops have been
measured in a 16.5-mm-diameter (0.652-in.-diameter) copper tube. Flow rates
varied from a critical velocity (minimum flow to prevent settling and dropout of
Slush Hydrogen 155

solid particles) of 0.45 mls (1.5 fils) to as high as 13.7 mls (45 fils). For flows with
a solid mass fraction of 0.3, the pressure drop was less than that with TP liquid
hydrogen for flow rates less than 3.66 mls (12 fils). With higher solid mass fractions,
the pressure drop was as much as 20% greater than for TP liquid hydrogen.27
Flow rates must be sufficient to maintain the integrity of the slush without
allowing any settling of the solid particles that would cause them to block either
the line itself or any side entrances such as for instrumentation ports or relief valves.
Proper system design must consider the sizes and orientations of transfer system
components and should be able to minimize any settling problems.

10.4.9.2. Upgrading and Replenishment


In some cases, it is possible that the desired fraction of solid in a storage vessel
will be higher than that initially supplied. In this case it will be necessary to upgrade
the solid fraction. Also, once the slush has left the slush generator and is transferred
to the storage tank, the heat leaking into the system will reduce the solid fraction.
F or both of these reasons, it will be necessary to provide a means of increasing the
soiid fraction of the slush in the storage tank. A method for doing so would be to
provide a continuous flow of slush into the storage tank while a return stream of
liquid hydrogen (at the TP temperature) is returned to the supply tank. This method
requires a filter in the tank being upgraded to prevent the return of the solid. The
safety concerns as well as the actual operation of the system are dependent upon
the flow through the filter occurring continuously without any blockage taking
place because of solid particles at the filter entrance. Any blockage could be serious
in itself. However, this same mechanism would also allow the accumulation and
concentration of any solid air particles that had previously entered the slush. The
accumulation of solid air could create a dangerous situation out of a previously
innocuous one or could exacerbate a previously hazardous situation. It will be
necessary to devise detection schemes and contingency procedures to alleviate any
such possibility.

10.4.9.3. Ullage Gas Requirements for Storage of Slush Hydrogen

In order to guarantee the maintenance of the storage system pressure above


that of the atmosphere, storage of slush hydrogen will require a supply of ullage
gas. This can either be a supply of hydrogen gas, in the case where thermal gradients
can be maintained in the liquid above the solid level, or helium gas, in the case
where it cannot. In either case, the pressure-monitoring system and the rate of gas
supply must be able to respond rapidly to maintain the desired pressure in the
storage tank.
156 Chapter 10

10.5. CONCLUSION

Several conclusions are possible concerning safe handling of slush hydrogen.


Slush hydrogen presents a new degree of difficulty of handling. From a cryogenic
standpoint, this fluid will present a difficulty of handling more like that of liquid
helium than that of liquid hydrogen.
A number of safety problems arise that require further investigation before the
safety problems can be fully understood. Some of these problems will require
experimental work as well as analytical examination (see Section 12.4). The work
that has been done on slush hydrogen to date is a significant step forward and has
formed the basis for understanding what remains to be done. Provided that the
proper precautions are taken and that the necessary research work is performed, it
should be possible to handle slush hydrogen safely.

REFERENCES

I. Edeskuty, E J., Stewart, W. E, and Mann, D. B. (1991). Slush Hydrogen Safety, NASP Technical
Memorandum 1145, NASA Langley Research Center, Langley, Virginia.
2. Roder, H. M. (1977). The Thennodynamic Properties of Slush Hydrogen and Oxygen, NBSIR
77-859, U.S. National Bureau of Standards, Boulder, Colorado.
3. McCarty, R. D., Hord, J., and Roder, H. M. (1981). Selected Properties of Hydrogen (Engineering
Design Data), NBS Monograph 168, U.S. Department of CommercefU.S. National Bureau of
Standards, Washington, D.C.
4. Mullins, J. C., Ziegler, W. T., and Kirk, B. S. (1961). The Thennodynamic Properties of
Parahydrogen from I to 22 K, Technical Report No.1, Project No. A-593, Engineering Experiment
Station, Georgia Institute of Technology, Atlanta, Georgia.
5. Willis, W. L. (1966). Electrical conductivity of some cryogenic fluids, Cryogenics 6 (October),
279.
6. Scott, R. B. (1988). Cryogenic Engineering, Met-Chern Research Inc., Boulder, Colorado.
7. Scott, R. B., Brickwedde, E G., Urey, H. C., and Wahl, M. H. (1934). J. Chern. Phys. 2, 454.
8. Farkas, A. (1935). Orthohydrogen and Heavy Hydrogen, Cambridge University Press, Cambridge,
England.
9. Greene, N. E., and Sonntag, R. E. (1968). Solid-liquid-vapor equilibrium in the system hydro-
gen-helium, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 13, pp.
357-362, Plenum Press, New York.
10. Smith, S. R. (1952). Gas-Liquid Phase Equilibrium in the He-H2 System, Ph.D. Thesis, Ohio
State University, Columbus, Ohio.
II. Street, W. B., Sonntag, R. E., and Van Wylen, G. J. (1964). Liquid-vapor equilibrium in the system
nonnal hydrogen-helium, J. Chern. Phys. 40, 1390.
12. Laquer, H. L. personal communication.
13. Edeskuty, E J., and Williamson, K. D., Jr. (1977). Liquid hydrogen storage and transmission, in
Hydrogen: Its Technology and Implications (K. E. Cox and K. D. Williamson, Jr. eds.), Vol. II,
Chap. 3, CRC Press, Boca Raton, Florida.
14. Gu, Y., and Timmerhaus, K. D. (1994). Experimental verification of stability characteristics for
thennal acoustic oscillations in a liquid helium system, in Advances in Cryogenic Engineering (p.
Kittel, ed.), Vol. 39, pp. 1733-1748, Plenum Press, New York.
Slush Hydrogen 157

15. Ludtke, P. R. (1970). Slush Hydrogen Flow Facility, U.S. National Bureau of Standards Report
9752, Boulder, Colorado.
16. Arthur D. Little, Inc. (1961). Final Report, Electrostatic Hazards Associated with the Transfer and
Storage of Liquid Hydrogen, Report to the Agena and Centaur Systems Office, Marshall Space
Flight Center, National Aeronautics and Space Administration, Huntsville, Alabama.
17. Mann, D. B., Ludtke, P. R., Sindt, C. F., Chelton, D. B., Daney, D. E., and Pollack, G. L. (1965).
Characteristics of Liquid-Solid Mixtures of Hydrogen at the Triple Point, U.S. National Bureau
of Standards Report 8881, Boulder, Colorado.
18. Sindt, C. F. (1970). A summary of the characterization study of slush hydrogen, Cryogenics, 10(5),
372-380.
19. Voth, R. O. (1978). Producing liquid-solid mixtures of hydrogen using an auger, U.S. National
Bureau of Standards Report NBSIR 78-875, Boulder, Colorado.
20. Voth, R. 0., Ludtke, P. R., and Brennan, J. A. (1990). Producing slush hydrogen with a small auger,
National Aero-Space Plane Technical Memorandum 1099, National Aeronautics and Space
Administration Langley Research Center, Langley, Virginia.
21. Waynert, J. A., Barclay, J. A., Claybaker, C., Foster, R. w., Jaeger, S. R., Kral, S., and Zimm, C.
(1988). Production of slush hydrogen using magnetic refrigeration, in Proceedings of the 7th
Intersociety Cryogenics Symposium of the ASME, Houston, Texas, Jan. 22-25, 1989 (C. E
Gottzmann, L. C. Kun, K. D. Timmerhaus, and L. Wenzel, eds.), The American Society of
Mechanical Engineers, New York.
22. Military Specification, Propellant, Hydrogen, MIL-P-2720lB (1971).
23. Compressed Gas Association (1990). CGA G-5.3, Commodity Specification for Hydrogen,
Compressed Gas Association, Arlington, Virginia.
24. Scott, L. E., Robbins, R. E, Mann, D. B., and Birmingham, B. W. (1960). Temperature stratification
in a nonventing liquid helium Dewar, J. Res. 64C(I), 19.
25. Mann, D. B., Sindt, C. E, Ludtke, P. R., and Chelton, D. B. (1966). Slush Hydrogen Fluid
Characterization and Instrumentation Analysis, U.S. National Bureau of Standards Report 9265,
Boulder, Colorado.
26. Daney, D. E., Ludtke, P. R., Cheiton, D. B., and Sindt, C. E (1968). Slush Hydrogen Pumping
Characteristics, U.S. National Bureau of Standards Technical Note 364, Boulder, Colorado.
27. Sindt, C. E, Ludtke, P. R., and Daney, D. E. (1969). Slush Hydrogen Fluid Characterization and
Instrumentation, U.S. National Bureau of Standards Technical Note 377, Boulder, Colorado.
Chapter 11

Guidelines, Standards, and Regulations

Many documents, both fonnal and infonnal, exist to advise on or specify methods
for the design, construction, and operation of cryogenic systems. These documents
are variously known as rules, guidelines, standards, codes, and regulations, and any
of them can address any facet of the handling of a cryogenic fluid. A general goal
of all of these documents is to minimize risk of injury to personnel and damage to
facilities and to promote safety by infonning all interested parties of required,
accepted, and preferable methods of proceeding when working with a cryogenic
fluid.
Although there might be more than one safe way to carry out a given task, it
must be borne in mind that most systems will consist of pieces of equipment
manufactured by different sources and also will have to interact with other systems
that might have been built under different circumstances or might be operated by
personnel from different organizations or, even within the same organization, by
workers with different backgrounds. For this reason it is both desirable and safer
to standardize methods of design, construction, and operation to the maximum
extent possible.
All of the documents described in this chapter have been generated by people
with a considerable amount of experience, and usually the infonnation within the
text of these documents represents the consensus of a number of knowledgeable
individuals. Whenever the advice is applicable, it should be seriously considered and
followed unless there is a good reason for not doing so. Deviations from established
practices frequently lead to problems, and quick fixes by inexperienced personnel have
often resulted in accidents. Some examples are described in Chapter 13.
In this chapter the less precise word "rule" will not be used. Instead, we will
focus on guidelines, standards, codes, and regulations. In general, guidelines and
standards are consensus documents that can originate from anyone of a number of
different organizations and do not have the force of law in their application. All
such documents are intended to guide operation within a given sphere of work and,
by themselves, do not have the force of law, requiring mandatory compliance. A
body having the necessary authority can make compliance to a guideline or standard
159
160 Chapter 11

mandatory, and thus they become included in a regulation. The word "code" has
been applied to both nonmandatory and mandatory documents.
The most all-encompassing authority in the United States is contained in the
Code of Federal Regulations (CFR), into which any of the above-mentioned
documents can be incorporated, thereby making compliance to them mandatory. In
addition, the individual states as well as municipalities can also add regulations.
Within this framework, organizations can make more specific requirements per-
taining to their own operations. While these latter might not have the force oflaw,
one's employment is usually contingent upon obeying these requirements.
Thus, there are many layers of safety controls that impact upon the operation
of cryogenic systems. Those that are mandatory must be obeyed, and those that are
not are still of great value and should be considered. In some cases, the multiplicity
of the various regulations can become very complicated to follow.

11.1. GUIDELINES AND STANDARDS

Guidelines are technical information about safe practices and procedures


developed by organizations (e.g., NASA, the national laboratories, and industries)
for their own needs. These organizations assign technically qualified personnel (or
committees) to evaluate hazards, assemble information, and develop guidelines to
minimize risk in their operations. 1 These guidelines are not widely disseminated,
but copies are usually available upon request and constitute a valuable source of
safety information. Although such guidelines do not have the force of law, each
organization can and does enforce compliance to them within its own authority.
Safety standards and codes help identify and solve safety, health, and environ-
mental problems. Many of today's safety standards in the United States were
created between 1894 and 1918 as a result of public pressure and concern over
numerous accidents, including fatal fires, boiler explosions, elevator mishaps, and
failures of faulty construction. The Underwriters' Laboratory (UL) had its begin-
ning in 1894, and the National Fire Protection Association (NFPA) was founded in
1896. The American Society for Testing and Materials (ASTM) began in 1898. In
1905 the National Board of Fire Underwriters created the first National Building
Code. In 1918 the American National Standards Institute (ANSI) began its primary
function of acting as a clearinghouse for safety standards, known as "American
National Standards." The ANSI resulted from an agreement of several professional
societies, such as the American Society of Mechanical Engineers (ASME). It coordi-
nates the activities of associations and groups writing the standards in the United States.
Thus, the ANSI reviews standards submitted for consideration as consensus National
Standards by such organizations as the NFPA, ASTM, and ASME?
The safety standards (sometimes referred to as "codes") are consensus safety
documents that are developed by nonprofit trade associations, professional socie-
Guidelines, Standards, and Regulations 161

ties, or standards-making and -testing bodies that serve industrial, commercial, and
public needs. Organizations that originate standards include the following:
American Society of Mechanical Engineers (ASME)
American National Standards Institute (ANSI)
American Society for Testing and Materials (ASTM)
Compressed Gas Association (CGA)
Factory Mutual Engineering and Research (FM)
Instrument Society of America (lSA)
National Fire Protection Association (NFPA)
Underwriters' Laboratory (UL)
They are empowered to include advisory provisions or provisions that are intended
to become mandatory if adopted by authorized regulatory agencies.
The writing of a standard is usually initiated when a need is recognized by
members of nationally recognized organizations. The efforts involve a review of
available information, from which the scope of the proposed standard is developed.
A tentative version is usually published for review and comment by interested
persons and those affected by it. The comments are evaluated, and, if needed, a new
tentative version is prepared. Finally, the authorship committee and then a govern-
ing board both must vote to accept or reject the proposed standard. l
The ANSI defines a standard as "a generally agreed upon set of criteria
specifically designed to define a safe product, practice, mechanism, arrangement,
process, or environment based on currently available scientific and experimental
knowledge concerning the subject or scope of the standard.,,3 A key word in this
definition is "currently." As technology advances in the field of safety, to remain
effective so must the codes and standards be reviewed and modified to reflect any
necessary changes.
The ANSI is the coordinator of America's voluntary standards systems. The
ANSI also coordinates and manages representation of U.S. voluntary standards
interests in nongovernmental international standards organizations. The major ones
are the International Organization for Standardization (ISO) and the International
Electrotechnical Commission (1EC). ANSI is the official member ofboth.4
The NFPA is a nonprofit, technical and educational organization that promotes
improvements in fire protection and prevention. One of the activities of the NFPA
is the development of codes and standards to enhance fire safety. There are over
275 such standards. These standards are consensus documents that are generated
by technical committees composed of a broad range of interested groups such as
the following:
Manufacturers
Users
Consumers
162 Chapter 11

Research/testing
Special experts
Enforcers
Installers/maintainers
Labor
Insurance
The NFPA standards are reviewed and revised on a scheduled basis. Individuals
and organizations have the opportunity to present proposals for the standards
through a public adoption process. 5

Table 11.1. Selection of ASME Codes and Standards Applicable to Cryogenic Systemsa

ASME designation Title


Boiler and Pressure Vessel Code (see Table 11.3)
BI9.1-1990 Safety Standard for Air Compressor Systems
BI9.3-1991 Safety Standard for Compressors for Process Industries
BI6.5-1988 Pipe Flanges and Flanged Fittings
B 16.20-1993 Metallic Gaskets for Pipe Flanges-Ring Joint, Spiral-Wound, and
Jacketed
BI6.21-1992 Nonmetallic Flat Gaskets for Pipe Flanges
BI6.22-1989 Wrought Copper and Copper Alloy Solder Joint Pressure Fittings
BI6.33-1990 Manually Operated Metallic Gas Valves for Use in Gas Piping
Systems up to 125 psig (Sizes 112 through 2)
B31 Pressure Piping (see Table 11.2)
B40.1-1991 Gauges-Pressure Indicating Dial Type--Elastic Element
B96.1-1993 Welded Aluminum-Alloy Storage Tanks
CSD-I-1992 Controls and Safety Devices for Automatically Fired Boilers
MFC-3M-1989 Measurement of Fluid Flow in Pipes Using Orifice, Nozzle and Venturi
MFC-4M-1986 Measurement of Gas Flow by Turbine Meters
MFC-7M-1987 Measurement of Gas Flow by Means of Critical Flow Venturi Nozzles
PTC 3.3-1969 (RI992) Gaseous Fuels
PTC4.3-1968 (RI991) Air Heaters
PTC 7.1-1962 (RI969) Displacement Pumps
PTC 8.2-1990 Centrifugal Pumps
PTC 9-1970 (RI992) Displacement Compressors, Vacuum Pumps and Blowers
PTC 10-1965 (RI992) Compressors and Exhausters
PTC 19.1-1985 (RI990) Instruments and Apparatus: Part I Measurement Uncertainty
PTC 19.2-1987 Instruments and Apparatus: Part 2 Pressure Measurement
PTC 19.3-1974 (1986) Temperature Measurement
PTC 19.16-1965 Density Determinations of Solids and Liquids
PTC 25.3-1988 Safety and Relief Valves
PVHO-I-1993 Safety Standard for Pressure Vessels for Human Occupancy

a Ref. 6.
Guidelines, Standards, and Regulations 163

Table 11.2. Selection of Standards from the ASME Code for Pressure Piping"

ASME designation Title


Al3.l Scheme for the Identification of Piping Systems
B3lG Manual for Determining the Remaining Strength of Corroded
Pipelines: A Supplement to B31, Code for Pressure Piping
B3l.l Power Piping
B31.2 Fuel Gas Piping
B31.3 Chemical Plant and Petroleum Refinery Piping
B31.4 Liquid Transportation Systems for Hydrocarbons, Liquid Petroleum
Gas, Anhydrous Ammonia, and Alcohols
B31.5 Refrigeration Piping
B31.8 Gas Transmission and Distribution Piping Systems
B31.9 Building Services Piping
B31.11 Slurry Transportation Piping Systems

a Ref. 6.

A selection of ASME Codes and Standards applicable to cryogenic systems is


given in Table 11.1. 6 The ASME Code for Pressure Piping,6 summarized in Table
11.2, is an important one for cryogenic systems; in particular, B31.3, Chemical
Plant and Petroleum Refinery Piping, is typically specified as a standard for the
identification, design, and welding of cryogenic piping. Another important ASME
standard is the ASME Boiler and Pressure Vessel Code, summarized in Table 11.3. 6
Section VIII of this standard is commonly specified for cryogenic vessels.
The ASTM has grown into one of the largest voluntary standards development
systems in the world. ASTM is a not-for-profit organization that provides a forum
for producers, users, ultimate consumers, and those having a general interest
(representatives of government and academia) to meet on common ground and
write standards for materials, products, systems, and services. A standard, as used
in ASTM, is a document that has been developed and established within the
consensus principles of the society and that meets the approval requirements of
ASTM procedures and regulations. The term "standard" serves in ASTM as an
adjective in the title of documents, such as test methods or specifications, to connote
specified consensus and approval. 7 A summary of ASTM Standards is given in
Table 11.4. 8 Some ANSI standards that are applicable to cryogenic systems are
given in Table 11.5, and some standards of the American Petroleum Institute (API)
are listed in Table 11.6. A selection ofNFPA standards is provided in Table 11.7. A
sampling of Loss Prevention Data Sheets of Factory Mutual Engineering and
Research is given in Table 11.8. Some representative standards of the CGA are listed
in Table 11.9. Some examples of industrial guidelines are given in Table 11.10.
164 Chapter 11

Table 11.3. Outline ofthe ASME Boiler and Pressure Vessel Codea

Section Title
I Power Boilers
II Materials
Part A Ferrous Material Specifications
PartB Nonferrous Material Specifications
PartC Specifications for Welding Rods, Electrodes and Filler Metals
PartD Properties
III Rules for Construction of Nuclear Power Plant Components
Subsection NCA General Requirements for Division I and Division 2
Division I
Subsection NB Class I Components
Subsection NC Class 2 Components
Subsection ND Class 3 Components
Subsection NE Class MC Components
Subsection NF Component Supports
Subsection NG Core Support Structures
Appendices
Division 2 Code for Concrete Reactor Vessels and Containments
IV Heating Boilers
V Nondestructive Examination
VI Recommended Rules for the Care and Operation of Heating Boilers
VII Recommended Guidelines for the Care of Power Boilers
VIII Pressure Vessels
Division 1 Rules for Construction of Pressure Vessels
Division 2 Alternative Rules
IX Welding and Brazing Qualifications
X Fiber-Reinforced Plastic Pressure Vessels
XI Rules for Inservice Inspection of Nuclear Power Plant Components
Code Cases Boilers and Pressure Vessels
Code Cases Nuclear Components

a Ref. 6.

Table 11.4. Summary of ASTM Standardsa

Section and volume Title


Section I Iron and Steel Products
Volume 01.01 Steel-Piping, Tubing, Fittings
01.02 Ferrous Castings; Ferroalloys
01.03 Steel-Plate, Sheet, Strip, Wire
01.04 Steel-Structural, Reinforcing, Pressure Vessel, Railway
01.05 Steel-Bars, Forgings, Bearing, Chain, Springs
01.06 Coated Steel Products
01.07 Shipbuilding
(continued)
Guidelines, Standards, and Regulations 165

Table 11.4. (Continued)

Section and volume Title


Section 2 Nonferrous Metal Products
Volume 02.01 Copper and Copper Alloys
02.02 Aluminum and Magnesium Alloys
02.03 Electrical Conductors
02.04 Nonferrous Metals-Nickel, Cobalt, Lead, Tin, Zinc, Cadmium,
Precious, Reactive, Refractory Metals and Alloys
02.05 Metallic and Inorganic Coatings; Metal Powders, Sintered P/M
Structural Parts
Section 3 Metals Test Methods and Analytical Procedures
Volume 03.01 Metals-Mechanical Testing; Elevated and Low-Temperature Tests;
Metallography
03.02 Wear and Erosion; Metal Corrosion
03.03 Nondestructive Testing
03.04 Magnetic Properties; Metallic Materials for Thermostats, Electrical
Heating and Resistance, Contacts, and Connectors
03.05 Analytical Chemistry for Metals, Ores, and Related Materials (I): A 751-
E354
03.06 Analytical Chemistry for Metals, Ores, and Related Materials (II): E356--
latest; Surface Analysis
Section 4 Construction
Volume 04.01 Cement; Lime; Gypsum
04.02 Concrete and Aggregates
04.03 Road and Paving Materials; Pavement Management Technologies
04.04 Roofing, Waterproofing, and Bituminous Materials
04.05 Chemical-Resistant Materials; Vitrified Clay, Concrete, Fiber-Cement
Products; Mortars; Masonry
04.06 Thermal Insulation; Environmental Acoustics
04.07 Building Seals and Sealants; Fire Standards, Building Constructions
04.08 Soil and Rock; Dimensional Stone; Geosynthetics
04.09 Wood
Section 5 Petroleum Products, Lubricants, and Fossil Fuels
Volume 05.01 Petroleum Products and Lubricants (I): D56--D2596
05.02 Petroleum Products and Lubricants (II): D2597-D4629
05.03 Petroleum Products and Lubricants (III): D436--latest; Catalysts
05.04 Test Methods for Rating Motor, Diesel, and Aviation Fuels
05.05 Gaseous Fuels; Coal and Coke
Section 6 Paints, Related Coatings, and Aromatics
Volume 06.01 Paint-Tests for Chemical, Physical, and Optical Properties;
Appearance; Durability of Nonmetallic Materials
06.02 Paint-Products and Applications; Protective Coatings; Pipeline
Coatings
06.03 Paint-Pigments, Drying Oils, Polymers, Resins, Naval Stores,
Cellulosic Esters, and Ink Vehicles
06.04 Paint-Solvents; Aromatic Hydrocarbons
(continued)
166 Chapter 11

Table 11.4. (Continued)

Section and volume Title


Section 7 Textiles
Volume 07.01 Textiles (I): D76--D3219
07.02 Textiles (II): D3333--latest
Section 8 Plastics
Volume 08.01 Plastics (I): C 177-D 1600
08.02 Plastics (II): D1601-D3099
08.03 Plastics (Ill): D3100-latest
08.04 Plastic Pipe and Building Products
Section 9 Rubber
Volume 09.01 Rubber, Natural and Synthetic-General Test Methods; Carbon Black
09.02 Rubber Products, Industrial-Specifications and Related Test Methods;
Gaskets; Tires
Section 10 Electrical Insulation and Electronics
Volume 10.01 Electrical Insulation (I}-D69-D2484
10.02 Electrical Insulation (II}-D2518-latest
10.03 Electrical Insulating Liquids and Gases; Electrical Protective Equipment
10.04 Electronics (I)
10.05 Electronics (II)
Section II Water and Environmental Technology
Volume 11.01 Water (I)
11.02 Water (II)
11.03 Atmospheric Analysis; Occupational Health and Safety; Protective
Clothing
11.04 Pesticides; Resource Recovery; Hazardous Substances and Oil Spill
Responses; Waste Management; Biological Effects
Section 12 Nuclear, Solar, and Geothennal Energy
Volume 12.01 Nuclear Energy (I)
12.02 Nuclear Energy (II), Solar, and Geothennal Energy
Section 13 Medical Devices and Services
Volume 13.01 Medical Devices; Emergency Medical Services
Section 14 General Methods and Instrumentation
Volume 14.01 Analytical Methods--Spectroscopy; Chromatography; Computerized
Systems
14.02 General Test Methods, Nonmetal; Laboratory Apparatus; Statistical
Methods; Forensic Sciences
14.03 Temperature Measurement
Section 15 General Products, Chemical Specialties, and End Use Products
Volume 15.01 Refractories; Carbon and Graphite Products; Activated Carbon
15.02 Glass; Ceramic Whitewares
15.03 Space Simulation; Aerospace and Aircraft; High Modulus Fibers and
Composites
15.04 Soap; Polishes; Leather; Resilient Floor Coverings
(continued)
Guidelines, Standards, and Regulations 167

Table 11.4. (Continued)

Section and volwne Title


15.05 Engine Coolants; Halogenated Organic Solvents
15.06 Adhesives
15.07 End Use Products
15.08 Fasteners
15.09 Paper; Packaging; Flexible 8arrier Materials; 8usiness Imaging Products
Section 00 Index
Volwne 00.01 Subject Index and Alphanwneric List

aRef.8.

Table 11.5. Selection of ANSI Standards

ANSI designation Title


Al3.1 Scheme for the Identification of Piping Systems
816.5 Standard for Steel Pipe Flanges and Flanged Fittings
831 Code for Pressure Piping
831.1 Code for Power Piping
831.2 Code for Pressure Piping
831.3 Chemical Plant and Petroleum Refinery Pipmg
831.5 Refrigeration Piping
831.8 Gas Transmission and Distribution Piping Systems
857.1 Compressed Gas Cylinder Valves
CI National Electrical Code
Z41.1 Safety Toe Footwear
Z87.1 Occupational and Educational Eye and Face Protection
Z292.2 Gaseous Hydrogen Systems at Consumer Sites
Z292.3 Liquefied Hydrogen Systems at Consumer Sites
ANSI 19.3 Safety Standards for Compressors for Process Industries
ANSI 836.19 Stainless Steel Pipe
ANSI 895.1 Terminology for Pressure Relief Devices
ANSI C2 National Electrical Safety Code
ANSI K61.1 Safety Requirements for the Storage and Handling of Anhydrous
Ammonia
ANSIZII7.1 Safety Requirements for Working in Tanks and Other Confined
Spaces
ANSI Z223.1 Gas Code, National Fuel
ANSI!API 2510 Design and Construction ofLP-Gas Installations at Marine and
Pipeline Terminals, Natural Gas Processing Plants, Refineries, and
Tank Farms
ANSI!ASHRE 15-78 Safety Code for Mechanical Refrigeration
ANSI!ASME PTC-I Performance Test Codes, General Instructions
ANSI!ASME PTC-2 Performance Test Codes, Definitions and Values
(continued)
168 Chapter 11

Table 11.5. (Continued)

ANSI designation Title


ANSI/ASME PTC9 Perfonnance Test Codefr-Displacement Compressors, Vacuum
Pumps and Blowers
ANSI/ASME PTC-1O Perfonnance Test Code~ompressors and Exhausters
ANSI/ASME PVHO-I Safety Standard for Pressure Vessels for Human Occupancy
ANSI/ASTM C549-73 Specification for Perlite Loose Fill Insulation
ANSIIASTM C61O-67 Specification for Expanded Perlite Block and Pipe Thennal Insulation
ANSIIASTM C740-73 Practice for Evacuated Reflective Insulation in Cryogenic Service
ANSIIASTM D1835-76 Specifications for Liquefied Petroleum (LP) Gases
ANSI/ASTM D2512-70 Method of Test for Compatibility of Materials with Liquid Oxygen
(Impact Sensitivity Threshold Technique)
ANSIIASTM D3442-75 Method of Test for Tritium in Air
ANSI!ASTM E595 Test for Total Mass Loss and Collected Volatile Condensable
Materials from Outgassing in a Vacuum Environment
ANSI!ASTM F78-79 Calibration of Helium Leak Detectors by Use of Secondary Standards
ANSI!ASTM F31 0-70 Sampling Cryogenic Aerospace Fluids
ANSI/ASTM F519-77 Hydrogen Embrittlement Testing of Aerospace Materials
ANSIIASTM G63-80 Evaluating Materials for Oxygen Service
ANSI/CGA G-7.1 Commodity Specification for Air
ANSIIIEEE C2 61-77 National Electrical Safety Code Interpretations, 1961-1977 Inclusive
ANSIIIEEE C2 78-80 National Electrical Safety Code Interpretations, 1978-1980
ANSIINFPA 30 Flammable and Combustible Liquids Code
ANSIINFPA 50A Gaseous Hydrogen Systems at Consumer Sites
ANSIINFPA 50B Liquefied Hydrogen Systems at Consumer Sites
ANSIINFPA 53M Manual on Fire Hazards in Oxygen-Enriched Atmospheres
ANSUNFPA58 Storage and Handling of Liquefied Petroleum Gases
ANSIINFPA 70 National Electrical Code
ANSUNFPA 385 Flammable and Combustible Liquid Tank Vehicles
ANSI/ASQCCI General Requirements for a Quality Program
ANSI!ASQC Z1.I5 Generic Guidelines for Quality Systems
ANSIISAE AMS 30 I 0 Hydrogen, Liquid-High Purity, Propellant Grade
ANSIISAE AMS 3012 Oxygen, Liquid---Propellant Grade
ANSIISAE AMS 3015 Nitrogen, Liquid-Propellant Grade
ANSIIUL 144 Safety Standard for Pressure Regulating Valves for LP-Gas
ANSIlUL873 Safety Standard for Temperature-Indicating and -Regulating
Equipment
ANSIIUL441 Safety Standard for Gas Vents
ANSIlUL641 Safety Standard for Low-Temperature Venting Systems
Guidelines, Standards, and Regulations 169

Table 11.6. Some Standards of the American Petroleum Institute (API)

API designation Title


API 620 Recommended Rules for Design and Construction of Large, Welded,
Low-Pressure Storage Tanks
API 2510A Design and Construction of LNG Installations at Marine and Pipeline
Terminals, Natural Gas Processing Plants, Refineries, and Other
Industrial Plants
API 510 Maintenance, Rating, Repair and Alteration

Table 11.7. Selected Standards of the National Fire Protection Association (NFPA)

NFPA designation Title


NFPA I Fire Prevention Code
NFPA 13 Installation of Sprinkler System
NFPA30 Flammable and Combustible Liquids
NFPA37 Installation and Use of Stationary Combustion Engines and Gas
Turbines
NFPA45 Fire Protection in Laboratories Using Chemicals
NFPA50 Standard for Bulk Oxygen Systems at Consumer Sites
NFPA50A Gaseous Hydrogen Systems at Consumer Sites
NFPA50B Liquefied Hydrogen Systems at Consumer Sites
NFPA52 CNG Vehicular Fuel System
NFPA55 Handling of Compressed and Liquefied Gases in Portable Cylinders
NFPA58 Liquefied Petroleum Gas--Storage, Use
NFPA59 Liquefied Petroleum Gas-Utility Plants
NFPA59A Production, Storage, and Handling of Liquefied Natural Gas (LNG)
NFPA68 Guide for Venting of Deflagrations
NFPA69 Explosion Prevention Systems
NFPA 70 National Electrical Code
NFPA 77 Static Electricity
NFPA 78 Lightning Protection Code
NFPA80 Fire Doors and Windows
NFPA 101 Life Safety
NFPA220 Standard on Types of Building Construction
NFPA325M Fire Hazard Properties of Flammable Liquids, Gases, Volatile Solids
NFPA496 Purged and Pressurized Enclosures for Electrical Equipment in
Hazardous Locations
NFPA497A Classification of Class I Hazardous Location for Electrical Installation
in Chemical Plants
NFPA497M Classification of Gases, Vapors and Ducts for Electrical Equipment in
Hazardous Locations
Vols. 1&2 National Fire Codes
170 Chapter 11

Table 11.8. A Sampling of Loss Prevention Data Sheets of Factory Mutual Engineering
and Research

Loss prevention
data sheet no. Title
"Approval Guide," Factory Mutual System
1-20 Protection against Fire Exposure
1-44 Damage-Limiting Construction
2-8N Installation of Sprinkler Systems (NFPA)
5-1 Electrical Equipment in Hazardous (Classified) Locations
5-49 Gas and Vapor Detectors and Analysis Systems
7-0 Causes and Effects of Fires and Explosions
7-7 Semiconductor Fabrication Facilitiesa
7-14 Protection for Flammable Liquid/Flammable Gas Processing Equipment
7-17 Explosion Suppression Systems
7-29 Flammable Liquids in Drums and Small Containers
7-50 Compressed Gases in Cylindersb
7-52 Oxygen
7-53 Liquefied Natural Gas (LNG)
7-55112-28 Liquefied Petroleum Gas
7-83 Drainage for Flammable Liquids
7-88 Storage Tanks for Flammable Liquids

a Includes the use of hydrogen in semiconductor manufacture.


b Covers cylinder storage.

Table 11.9. Representative Standards of the Compressed Gas Association (CGA)

CGA designation Title


C-l Methods for Hydrostatic Testing of Compressed Gas Cylinders
C-7 Guide to Preparation of Precautionary Labeling and Marking of Compressed
Gas Containers
E-3 Pipeline Regulator Inlet Connection Standards
G-4 Oxygen
G-4.l Cleaning Equipment for Oxygen Service
G-4.3 Commodity Specification for Oxygen
G-4.4 Industrial Practices for Gaseous Oxygen Transmission and Distribution
Piping Systems
G-4.5 Commodity Specification for Oxygen Produced by Chemical Reaction
G-5 Hydrogen
G-5.2 Standard for Liquefied Hydrogen Systems at Consumer Sites
G-5.3 Commodity Specification for Hydrogen
G-5.4 Standard for Hydrogen Piping at Consumer Locations
(continued)
Guidelines, Standards, and Regulations 171

Table 11.9. (Continued)

CGA designation Title


G-9.1 Commodity Specification for Helium
G-IO.I Commodity Specification for Nitrogen
G-II.1 Commodity Specification for Argon
P-I Safe Handling of Compressed Gases in Containers
P-2.5 Transfilling of High Pressure Gaseous Oxygen to Be Used for Respiration
P-2.6 Transfilling of Liquid Oxygen to Be Used for Respiration
P-6 Standard Density Data, Atmospheric Gases and Hydrogen
P-7 Standard for Requalification of Cargo Tank Hose Used in the Transfer of
Compressed Gases
P-8 Safe Practices Guide for Air Separation Plants
P-9 The Inert Gases--Argon, Nitrogen and Helium
P-ll Metric Practice Guide for the Compressed Gas Industry
P-12 Safe Handling of Cryogenic Liquids
P-13 Safe Handling of Liquid Carbon Monoxide
P-14 Accident Prevention in Oxygen-Rich and Oxygen-Deficient Atmospheres
P-16 Recommended Procedures for Nitrogen Purging of Tank Cars
P-17 Procedures for Pneumatic Retesting of Cargo and Portable Tanks
P-18 Standard for Bulk Inert Gas Systems at Consumer Sites
P-19 Hazard Ratings for Compressed Gases
S-1.1 Pressure Relief Device Standards: Part I--Cylinders for Compressed Gases
S-1.2 Pressure Relief Device Standards: Part 2--Cargo and Portable Tanks for
Compressed Gases
S-1.3 Pressure Relief Device Standards: Part 3--Compressed Gas Storage
Containers
V-I American National, Canadian, and Compressed Gas Association Standard for
Compressed Gas Cylinder Valve Outlet and Inlet Connections
V-6 Standard Cryogenic Liquid Transfer Connections
V-6.l Standard Carbon Dioxide Transfer Connections
CGA-34I Standard for Insulated Cargo Tank Specifications for Cryogenic Liquids
SB-2 Oxygen-Deficient Atmospheres
SB-9 Recommended Practice for the Outfitting and Operation of Vehicles Used in
the Transportation and Transfilling of Liquid Oxygen to Be Used for
Respiration
TB-3 Hose Line Flashback Arrestors
HB-2 Handbook of Compressed Gases, Chapter 2, Regulatory Authorities for
Compressed Gases in United States and Canada; and Appendix A,
Summary of Selected State Regulations and Codes Concerning
Compressed Gases
172 Chapter 11

Table 11.10. Examples of Industrial Guidelines

Designation Title
Aireo Industrial Gases
AIG 1157 Safety and Carbon Dioxide in the Workplace
Air Products and Chemicals, Inc.
Safetygram-2 Gaseous Nitrogen
Safetygram-4 Gaseous Hydrogen
Safetygram-5 Gaseous Helium
Safetygram-6 Liquid Oxygen
Safetygram-7 Liquid Nitrogen
Safetygram-9 Liquid Hydrogen
Safetygram-IO Handling, Storage and Use of Compressed Gas Cylinders
Safetygram-II Emergency Action in Handling Leaking Compressed Gas Cylinders
Safetygram-12 Safe Handling and Use of Air Products Compressed Gases and Equipment
Safetygram-15 Cylinder Safety Devices
Safetygram-16 Safe Handling of Cryogenic Liquids
Safetygram-17 Dangers of Oxygen Deficient Atmospheres
Safetygram-18 Carbon Dioxide
Safetygram-19 Gaseous Carbon Monoxide
Safetygram-20 Nitrous Oxide
Linde Division, Union Carbide
EM 7212 Hydrogen Systems Electrical Safety
EN-13 Venting of Hydrogen and Other Lighter than Air Flammable Gases
F-9888-Q Liquefied Atmospheric Gases--Precautions and Safe Practices
Fll-572B Establishing Liquid Hydrogen Units at Customer Sites and Filling Stations
L-3499F Safety Precautions--Oxygen, Nitrogen, Argon, Helium, Carbon Dioxide,
Hydrogen, Fuel Gases, Ethylene Oxide, Sterilant Mixtures, Specialty
Gases
SA-5 Plant Design Safety
SA-35 Plant Fire Water Protection System

At present, there is no standard for the storage of cryogens in cryogenic storage


vessels. Although these vessels are almost always in capable and well-trained
hands, such a standard would be desirable. Work on an ANSI standard for cryogenic
piping (ANSI B31.1 0) was started but never completed.
The ISO is developing standards that will apply to the handling of cryogens
either jointly by two or more countries or in commerce between countries. The ISO
is a worldwide federation of national standards bodies, at present comprising 92
members, one in each of the participating countries. The scope of ISO covers
standardization in all fields except electrical and electronic engineering standards,
which are the responsibility oflEC, the International Electrotechnical Commission.
Guidelines, Standards, and Regulations 173

Table 11.11. Sampling ofISO Standards"

ISO number Title


1000 SI Units and Recommendations for the Use of Their Multiples and of Certain
Other Units
1101 Technical Drawings----Geometrical Tolerancing--Tolerancing of Form,
Orientation, Location and Run-Out-Generalities, Definitions, Symbols,
Indications on Drawings
1465 Aircraft-Liquid Oxygen Replenishment Coupling&-Mating Dimensions
1635 Wrought Copper and Copper Alloy&-Mating Dimensions
R1662 Refrigerating Plants Safety Requirements
2186 Fluid Flow in Closed Conduits--Connections for Pressure Transmissions
between Primary and Secondary Elements
2861 PT I Vacuum Technology~uick-Release Coupling&-Dimension&-Part I:
Clamped Type
2861 PT 2 Vacuum Technology~uick-Release Coupling&-Dimension&-Part 2:
Screwed Type
TR3313 Measurement of Pulsating Fluid Flow in a Pipe by Means of Orifice Plates,
Nozzles or Venturi Tubes
3529 PT I Vacuum Technology-Vocabulary-Part I: General Terms
3529PT2 Vacuum Technology--Vocabulary--Part 2: Vacuum Pumps and Related Terms
3529 PT 3 Vacuum Technology-Vocabulary-Part 3: Vacuum Gages
3933 Liquefied Petroleum Gas and Light Hydrocarbon&-Determination of Density
or Relative Density--Pressure Hydrometer Method
6184 PT 1 Explosion Protection System&-Part 1: Determination of Explosion Indices of
Combustible Dusts in Air
6184 PT 2 Explosion Protection System&-Part 2: Determination of Explosion Indices of
Combustible Gases in Air
6184 PT 3 Explosion Protection System&-Part 3: Determination of Explosion Indices of
Combustible FueVAir Mixtures Other than Dust!Air and Gas!Air Mixtures
6184 PT4 Explosion Protection System&-Part 4: Determination of Efficacy of
Explosion Suppression Systems
6758 Welded Steel Tubes for Heat Exchangers
6759 Seamless Steel Tubes for Heat Exchangers
TR7470 Valve Outlets for Gas Cylinder&-List of Provisions Which Are Either
Standardized or in Use
8010 Compressors for the Process Industry--Screw and Related Type&-
Specifications and Data Sheets for Their Design and Construction
80ll Compressors for the Process Industry--Turbo Typeir-Specifications and Data
Sheets for Their Design and Construction
8012 Compressors for the Process Industry-Reciprocating Type&-Specifications
and Data Sheets for Their Design and Construction
9000 Quality Management and Quality Assurance Standards----Guidelines for
Selection and Use
9000 PT I Quality Management and Quality Assurance Standard&-Part I: Guidelines for
Selection and Use
(continued)
174 Chapter 11

Table 11.11. (Continued)

ISO number Title


9000 PT 2 Quality Management and Quality Assurance Standards-Part 2: Generic
Guidelines for the Application ofISO 9001, ISO 9002 and ISO 9003
9000 PT 3 Quality Management and Quality Assurance Standards-Part 3: Guidelines for
the Application of ISO 9001 to the Development, Supply and Maintenance
of Software
9000 PT4 Quality Management and Quality Assurance Standards-Part 4: Guide to
Dependability Programme Management
9001 Quality Systems-Model for Quality Assurance in Design, Development,
Production, Installation and Servicing
9002 Quality Systems-Model for Quality Assurance in Production, Installation and
Servicing
9003 Quality Systems-Model for Quality Assurance in Final Inspection and Test
9004 Quality Management and Quality Systems Elements---Guidelines
9004PT I Quality Management and Quality Systems Elements-Part I: Guidelines
9004 PT2 Quality Management and Quality Systems Elements-Part 2: Guidelines for
Services
9004PT 3 Quality Management and Quality Systems Elements-Part 3: Guidelines for
Processed Materials
9004 PT4 Quality Management and Quality Systems Elements-Part 4: Guidelines for
Quality Improvement
9162 Petroleum Products-Fuels (Class F}-Liquefied Petroleum Gases-
Specifications
9803 Vacuum Technology-Pipeline Fittings-Mounting Dimensions
TR12100 PT 1 Safety of Machinery-Basic Concepts, General Principles for Design--Part I:
Basic Terminology, Methodology
TRI2100 PT2 Safety of Machinery--Basic Concepts, General Principles for Design--Part 2:
Technical Principles and Specifications
TR13763 Safety and Performance Criteria for Seamless Gas Cylinders

a Ref. 9.

Together, ISO and lEe form the specialized system for worldwide stand-
ardization--the world's largest nongovernmental system for voluntary industrial
and technical collaboration at the international level. The results of ISO technical
work are published in the form oflnternational Standards. There are, for example,
ISO standards for the quality grading of steel; for testing of the strength of
woven textiles; for storage of citrus fruits; for magnetic codes on credit cards;
for automobile safety belts; and for ensuring the quality and performance of
such diverse products as surgical implants, ski bindings, wire ropes, and
photographic lenses-to mention only a very few. A sampling of some ISO
standards is given in Table 11.11.9
Guidelines, Standards, and Regulations 175

11.2. CODES AND REGULATIONS

Regulations are directives established by official bodies authorized to create


safety requirements enforceable by political jurisdiction. In the United States on
the federal level, these official bodies include the U.S. Department of Transporta-
tion (US DOT) and the Occupational Safety and Health Administration (OSHA),
which can propose regulations or additions or modifications to sections of the CFR.
Recommendations of other government agencies and other interested parties are
also considered. Proposed regulations are usually published along with a descrip-
tion of the issues involved. Comments are sought and reviewed, and consideration
is also given to oral testimony given by interested parties. When final regulations
are published, provisions are made for interested parties to petition the officials to
amend or repeal these regulations. Often a specific cryogen is not mentioned by
name but is considered to be included by inference in these regulations. There are
several specialized organizations that are recognized as authorities through which
information can be disseminated, including

International Society of Fire Service Instructors


National Fire Protection Association
International Association of Fire Chiefs
International Association of Firefighters

States can also exercise a similar type of control, although such action is not
common. Many municipalities, however, control combustible cryogens by means
of fire ordinances.
"Adoption by Reference" or "Adoption by Transcription" are two common
methods by which a standard becomes part of a regulation. "Adoption by Refer-
ence" refers to the citing of the title of the standard and publishing information only.
"Adoption by Transcription" refers to the incorporation of the standard, in whole
orin part, into the text of the regulation.
Some elements of the U.S. Code of Federal Regulations are given in Table
11.12. Listings of some of the regulations in the CFR are presented in Appendix
A in Tables A.l, A.2, and A.3, which contain pertinent items from regulations
on liquefied natural gas facilities (Table A.l)1O and cryogenic liquid tank car
tanks (Table A.2) and OSHA regulations for handling flammable and combus-
tible liquids in the work place (Table A.3). These tables are mainly useful for
showing what types of regulations exist. Because more regulations can be added
or the regulations existing at the time of this writing can be changed or modified,
the most recently published CFR should be consulted directly for the most
current information.
176 Chapter 11

Table 11.12. Some Elements of the U.S. Code of Federal Regulations

Designation Title
IOCFR Energy
14CFR Aeronautics and Space
29CFR Labor
29 CFR 1910 Occupational Safety and Health
29 CFR 1910 Subpart H Hazardous Materials
29 CFR 1910.101 Compressed gases (general requirements)
29 CFR 1910.103 Hydrogen
29 CFR 1910.104 Oxygen
29 CFR 1910.106 Flammable and combustible liquids
29 CFR 1910.110 Storage and handling of liquefied petroleum gases
29 CFR 1910.1200 Hazard communication
29 CFR 1926 Safety and Health Regulations for Construction
29 CFR 1926.151 Fire prevention
29 CFR 1926.152 Flammable and combustible liquids
29 CFR 1926.153 Liquefied petroleum gas (LP-Gas)
33CFR Navigation and Navigable Waters
33 CFR 126 Handling of Class I (Explosive) Materials or Other Dangerous
Cargoes within or Contiguous to Water Front Facilities
46CFR Shipping
46CFR38 Liquefied Flammable Gases
46 CFR Subpart N Dangerous Cargoes
49CFR Transportation
49 CFR Subchapter C Hazardous Materials Regulations
49 CFR 178.57 Specification 4L; welded cylinders insulated
49 CFR 178.58 Specification 4DA; inside containers, welded steel for aircraft use
49 CFR 179 Specifications for Tank Cars
49 CFR 179 Subpart F Specification for Cryogenic Liquid Tank Car Tanks and Seamless
Steel Tanks
49 CFR 179.400 General specifications applicable to cryogenic liquid tank car
tanks
49 CFR 179.401 Individual specification requirements for cryogenic liquid tank
car tanks
49 CFR 179.500 Specification DOT-I07A; seamless steel tanks to be mounted on
or forming part of a car
49 CFR 192 Transportation of Natural and Other Gas by Pipeline
49 CFR 193 Liquefied Natural Gas Facilities: Federal Safety Standards
Guidelines, Standards, and Regulations 177

11.3. HYDROGEN STANDARDS AND REGULATIONS

The NFPA has a standard (NFPA 52) to cover compressed natural gas (CNG)
vehicular fuel systems but does not as yet have a similar one for hydrogen-fueled
vehicles. Bulk hydrogen systems have been in common usage for several decades
and have a safe operating history. This safety record can be attributed, at least in
part, to the appreciation of the installers and operating personnel for the potential
hazards associated with hydrogen. NFPA standards 50A and 50B apply to gaseous
and liquid hydrogen, respectively. These standards cover bulk hydrogen storage
systems from the point of the local fill connection to the point where the hydrogen
enters the customer's piping system. They do not cover either the delivery vehicle
or the distribution piping. A discussion of the philosophy of these two standards is
provided by Connolly. 11
The quantity-distance separation tables are the heart of these two documents.
An important factor, which is not stated directly in these documents, is that the
catastrophic failure of the storage vessel is not considered to be a credible event.
Thus, if a storage vessel were to fail catastrophically, the separation distances might
not be sufficient to prevent serious injury or property damage. Much greater
separation distances are specified by the Department of Defense (DOD) for liquid
hydrogen used as a propellant. 12,13 Thus, we have separation distances specified for
(1) the storage of liquid hydrogen, where the main safety consideration is release
and possible burning of hydrogen in air, and (2) the use of liquid hydrogen in an
experimental or testing facility as a propellant in conjunction with an oxidizer (such
as liquid oxygen), where the primary safety consideration is pressure rupture and/or
the rapid combustion, or detonation, of a hydrogen-oxidizer mixture.
Federal regulations applying to hydrogen are embodied primarily in the
49 CFR (DOT) and 29 CFR (OSHA). The DOT portions apply to the transportation
of hydrogen, and the OSHA portion applies to its safe handling in the work place.
The Transportation Safety Act of 1974 precipitated the reorganization of the
DOT and the concomitant revision of applicable regulatory codes. Equipment
specifications and shipping and carrier regulations for gaseous and liquid hydrogen
are given in the CFR, for example, 49 CFR 179 (see Table A.2 for a partial listing).
The CFR gives the federal regulations for the transportation of gaseous and liquid
hydrogen by highway, railroad, air, and water. The DOT classifies and treats
gaseous and liquid hydrogen as a compressed, flammable gas (see 49 CFR 172.101
and 49 CFR 172-179). The proper shipping name for liquid hydrogen is "HYDROGEN,
LIQUEFIED" (49 CFR 172.10 1). Air transportation of compressed hydrogen gas is
regulated by 49 CFR 172-178. Transportation of compressed hydrogen gas by
water is regulated by 49 CFR 172-179. Liquid hydrogen currently cannot be
shipped by either air or water. However, by special permit from the U.S. Coast
Guard, NASA has shipped liquid hydrogen by barge from Louisiana to Mississippi.
The DOT no longer issues these special permits but grants "exemptions" to the
178 Chapter 11

regulations for special shipments of hazardous materials (including liquid hydro-


gen). The Office of Hazardous Materials Operations of the DOT has the authority
to issue these exemptions and is planning to study the risk of shipping liquid
hydrogen by air. Much of the liquid-hydrogen production in the United States is
shipped by truck trailers via highway, which also requires exemptions.
An outline of OSHA regulations (29 CFR 1926.152) related to flammable and
combustible liquids is presented in Table A.3.

11.4. CONCLUSION

Gaining an understanding of the applicable regulations, codes, standards, and


guidelines is an arduous but absolutely necessary task. Usually, this is the preroga-
tive ofthe safety department or safety engineer in a organization; however, anyone
involved in cryogenics should be familiar with appropriate guidelines, standards,
and regulations. This effort is an ongoing one because of the updating of many of
the regulations as well as the continuing development of safety information.
International efforts are continuing to be made by the ISO to establish stand-
ards for the use of hydrogen across international borders. This is a necessary and
worthwhile effort, and one that becomes more important as the applications of
hydrogen technology increase.

REFERENCES

I. F. J. Edeskuty and N. N. Sheheen, eds. (1979). Critical Review and Assessment of Environmental
and Safety Problems in Hydrogen Energy Systems, Los Alamos Scientific Laboratory Report
LA-7820-PR, pp. 58-61, Los Alamos, New Mexico.
2. Siminski, V. J. (1987). Application of national consensus standards to pilot plant safety, Chern.
Eng. Prog. 83(1),60.
3. Anon. (1977). Safety standards, ProfeSSional Safety 1977 (August), Editorial.
4. American National Standards Institute (1982). 1982 Catalog of American National Standards,
American National Standards Institute, New York.
5. Bender, F. X. unpublished communication.
6. American Society of Mechanical Engineers (1995). 1995 ASME Publications Catalog, American
Society of Mechanical Engineers, Fairfield, New Jersey.
7. American Society for Testing and Materials (1992). Subject Index; Alphanumeric List, in 1992
Annual Book of ASTM Standards, Section 00, Vol. 00.01, American Society for Testing and
Materials, Philadelphia, Pennsylvania.
8. American Society for Testing Materials (1993). 1993 Annual Book of ASTM Standards, American
Society for Testing and Materials, Philadelphia, Pennsylvania.
9. International Organization for Standardization (1993). ISO Catalogue 1993, International Organi-
zation for Standardization, Geneva, Switzerland.
10. Liquefied Natural Gas Facilities: Federal Safety Standards, 49 CFR Part 193, Fed. Regist. 42(77),
Part m (April 21, 1977), pp. 20776-20800.
Guidelines, Standards, and Regulations 179

II. Connolly, W. W. (1966). A practical safety standard for commercial handling of liquefied
hydrogen, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 12, pp. 192-197,
Plenum Press, New York.
12. U.S. Department of Defense (1964). Quantity-Distance Storage Criteria for Liquid Propellants,
Department of Defense Directive 4145.21.
13. U.S. Department of Defense (1984). Ammunition and Explosives Safety Standards, Department
of Defense Directive 6055.9.
Chapter 12

Safety Problems Needing Further


Investigation

Safety is not an exact science but an ongoing process of improving, developing,


and applying new knowledge. As new projects stretch the frontiers of technology
(involving new or different experimentation and testing), new safety needs will be
disclosed. This occurred, for example, when the decision was made to use liquid
hydrogen as a rocket fuel and again when slush hydrogen was planned for use in
the National Aero-Space Plane. Each new project involves safety needs that have
many features in common with those of other projects, but usually it has needs
unique to that specific project.
Quite often, safety needs are not addressed until they have to be, and, because
of the expense of safety work (assessments, analyses, modeling, experiments, and
testing), safety research does not always get proper priority. It is not uncommon to
be making safety decisions involving uncertainties for which more information
would be most helpful-we find ourselves trying to get by without all the knowl-
edge needed.
In this chapter we describe some safety problems and uncertainties that we
have experienced, or that we know to have been encountered, in the cryogenics
field. A primary goal of any project is to complete the project in as safe a manner
as possible, and the fewer concerns about which adequate knowledge is not
available, the more confidence we have in being able to operate safely.

12.1. DISPERSION OF LEAKS AND SPILLS

The controlled venting of cryogen vapors such as the normal boil-off from a
cryogenic storage Dewar is not usually a problem. However, the unintended, rapid
release caused by a leak from a system under pressure or the spill of a large quantity
of a cryogenic fluid can give rise to a serious hazard. While other hazards might
arise, such as from cold embrittlement of nearby equipment (see Chapter 3), the
major concerns are the creation of a local atmosphere that does not support life
181
182 Chapter 12

(asphyxiation; see Chapter 2) and, in the case of combustible cryogens, such as


hydrogen or LNG, a fire or explosion.

12.1.1. Liquid-Cryogen Spills or Vapor Releases without Combustion


The spill or leak of a cryogenic fluid in a sufficient quantity to deplete the local
atmosphere in oxygen is a phenomenon that is in need of more study. The release
of any cryogen, other than oxygen, is of concern in this respect.
As described in Chapter 7, there are a number of factors that can influence the
dispersion and mixing of the local atmosphere. One of these factors is the buoyancy
of the gas that is diluting the atmosphere. All cryogenic liquids and gases at their
normal boiling temperature have a negative buoyancy with respect to air at I atm
(101 kPa) and 20C. This fact is illustrated in Table 12.1, which presents the
densities of the common cryogens that are likely to be involved in the type of release
that is considered here. Also listed are the temperatures at which these gases attain
a neutral buoyancy with respect to air.
One fact that must be remembered is that spill tests done with liquid hydrogen
have demonstrated that a major factor in the warming of a cold cryogenic fluid is
its mixing with the surrounding atmosphere. When warming is achieved by this
mechanism, the resulting gas mixture has an average density between that of the
cooled air and that of the warming cryogenic gas. Thus, neutral buoyancy will not
be achieved at the temperature listed in Table 12.1 if warming is effected in this
manner, and in this case one of the dispersing mechanisms will not be effective.
Thus, for a gas release, the temperature of the escaping gas is of importance, and a
sufficiently cold leak can tend to pool cold gas and form dangerous pockets in the
absence of strong convection currents. Obviously, the spill of a liquid cryogen can
present the same sort of hazard.
Therefore, the release of either gases or cryogenic liquids under confined
conditions such as within a room, and even outdoors under some circumstances,

Table 12.1. Buoyancy of Cryogens

Normal boiling Gas density at NBP Temperature of neutral


Cryogen temperature (K) (kg/m3) buoyancya (K)
Helium 4.2 16.9 40
Hydrogen 20.3 1.34 23
Nitrogen 77.3 4.62 284
b
Argon 87.3 5.77
b
Oxygen 90.2 4.47
Methane 111.6 1.82 165c

a Referred to air at 101 kPa and 20 e,with density of 1.20 kglmJ


b Oxygen and argon are heavier than air at 101 kPa and 20 e.
C LNG is not a single-component substance of pure methane but contains a number of other heavier, higher-boiling

constituents. Also, the temperature for methane is estimated.


Safety Problems Needing Further Investigation 183

requires further study. A model is needed to permit the dispersion analysis to be


made without a great expense. The model must be validated with experimental data.
In many situations, for example, the release of a cryogen in a long narrow room,
the assumption of a uniform dispersion of a gas release might lead to a false
conclusion that a room was safe to enter, when dangerous pockets of an atmosphere
depleted in oxygen could exist. The study should include releases of both cold gases
at various temperatures and liquids.

12.1.2. Liquid-Cryogen Spills or Vapor Releases with Possible Combustion


The release of a significant quantity of a combustible cryogen either as a liquid
or as a gas creates the possibility of a fire or explosion hazard. Although it is
generally believed that a hydrogen combustion in the open atmosphere will not lead
to a detonation, a large deflagration can lead to overpressures (see Section 13.2.1.2).
If a detonation were to occur, much greater damage could result (see Chapter 8).
The parameters of concern are the distance to which a combustible cloud could be
formed, the height that it could attain before it spreads and becomes sufficiently
diluted to be out of the combustibility range, and the total quantity of combustible
gas contained in the cloud. Factors involved in effecting the dispersion of the
combustible vapor cloud include the release momentum of the expelled gas or
liquid, atmospheric turbulence, wind velocity, plume buoyancy, and the turbulence-
inducing mechanism of the surrounding terrain. Some studies have been made,l)
but further experimental verification of the necessary assumptions is needed.
Several assessments can be suggested as appropriate for guiding future experi-
ments. These include:
1. Assessment ofthe consequences ofan unintended ignition ofa hydrogen cloud
2. Assessment ofthe methods for describing the dispersion of a hydrogen cloud
3. Assessment of the methods for describing and predicting vapor generation
from liquid-hydrogen spills on land or water
4. Assessment of the parameters involved in setting a recommended cross-
over point between the mere venting of hydrogen (unflared) and required
flaring of the effluent gas
In order to carry out the experimental work that might be suggested by these
assessments, it will be advantageous to develop better hydrogen detectors. These
detectors should be simple, rugged, versatile, and reliable. They should be able to
scan wide areas and be capable of measuring hydrogen concentrations at a distance.

12.2. SPILLS OF LIQUID CRYOGENS ONTO WATER SURFACES

Large quantities of LNG and liquid hydrogen are being transported by ships
and barges. The transport of any cryogen, including liquid hydrogen and LNG, by
184 Chapter 12

ship or by trucks or trains crossing rivers or lakes introduces the possibility of


cryogen spills onto a water surface.
The potentially high heat-transfer rates coupled with the large thermal capacity
of the water and low heats of vaporization of the cryogens give rise to rapid
expansion ofthe resulting vapors and the consequent potential hazard of a flameless
expanding vapor explosion. Experiments with LNG have resulted in "rapid phase
transition" explosions which were able to cause some damage to the test facility.
Also, the concern was expressed that the resulting shock wave might be sufficiently
energetic to ignite the combustible vapors.3

12.3. HYDROGEN COMBUSTION

The combustion of hydrogen has been studied by a number of investigators,


and their findings have been reported in the literature (see Chapter 8). However,
there remain considerations regarding the combustion of hydrogen that need better
understanding.

12.3.1. Ignition of Hydrogen Releases


It is commonly assumed that large accidental releases of hydrogen will be
accompanied by an ignition. However, it is not possible to predict whether or not
a given hydrogen release will ignite. When ignition does occur, it is not always
possible to identify the ignition source.
The Joule-Thomson coefficient is defined as (dT/ dP)H, where the subscript
H denotes constant enthalpy, and is equal to zero for an ideal gas. Even though
hydrogen is close to ideal at temperatures well above its normal boiling point, its
Joule-Thomson coefficient is only equal to zero along a definite path on a plot of
temperature versus pressure, the so-called inversion curve. For a given pressure,
the inversion temperature of a gas is that temperature above which the gas warms
upon constant-enthalpy expansion.4 The inversion temperature of hydrogen varies
from 28 K to 200 K depending upon pressure. s Because of the likelihood of a
gaseous hydrogen release being above this range, it is sometimes supposed that this
increase in temperature accompanying a hydrogen release will be sufficient to cause
ignition. However, the increase to be expected is only a few kelvins, and much too
small to raise the gas to its ignition temperature under most circumstances.
The possibility of shock-wave ignition of combustible hydrogen-air mixtures
has been mentioned as a possible ignition source. Also, the buildup of static electric
charge is frequently thought to be the cause of hydrogen ignition. Both of these
phenomena deserve a more complete investigation. Further information is also
needed on the ignition process for solid oxygen condensed in liquid or slush
hydrogen. How much energy is required, and what are the possible energy sources
capable of providing this amount of energy?
Safety Problems Needing Further Investigation 185

12.3.2. Venting versus Flaring


The planned release of a combustible gas or liquid must include a vent or flare
system. Typical examples of planned releases include such events as the normal
boil-off from a liquid-hydrogen Dewar, venting of boil-off gas during a cooling
operation, or even the operation of a safety reliefvalve. For most normal operations,
the vapors are usually only vented directly to the atmosphere (never inside a closed
room or confined area).
However, for some operations, larger or higher-rate venting is necessary.
This might be the case for some cooling operations like the rapid transfer of
liquid hydrogen into a precooled Dewar or one that is that is initially at room
temperature.
The question frequently arises conceming the vent rate above which is it
advisable to flare the hydrogen rather than to merely vent it, unburned, to the
atmosphere. The answer to this question will depend upon the three parameters
mentioned in Section 12.1.2, namely, the maximum distance that the combustible
plume can persist, its height, and the total inventory of hydrogen in the plume. Also,
an important consideration is the degree of isolation of the vent stack, that is, the
distance to which the plume can be isolated from potential ignition sources and
objects that can be damaged by an unexpected ignition of the plume.
Therefore, a guideline or standard for venting and flaring of hydrogen is
needed to cover the design and operation of ventiflare systems. The conditions that
govern the upper limit for nonflared release rates should be defined.
The operation offlare stacks has been studied and conditions for flame stability
have been established for a number of combustible gases, and these conditions must
also be considered in the design of a flare stack. 6

12.3.3. Transition of Deflagration to Detonation


The initiation of a hydrogen-air detonation has been studied, and the energy
necessary to initiate the detonation and the geometric conditions for it to persist
have been determined. 708 Further studies have shown that a hydrogen deflagration
can transit to a detonation if the conditions are proper. The transition requires
combustible mixtures closer to stoichiometric, and devices that can induce turbu-
lence in the flame front make the transition more likely8 (see Chapter 8). A
consideration of the incident described in Section 13.2.1.2 gives rise to the question
of whether a deflagration in the open atmosphere could transit to a detonation, given
a large enough combustion volume. Further investigation of the deflagration-to-
detonation transition seems warranted.

12.3.4. Thermal Effects of Hydrogen Combustion


A matter of concern is the fire hazard or damage potential from a hydrogen
fire. The percentage of thermal energy radiated from flame to surroundings for
186 Chapter 12

hydrogen and for methane is similar; however, because hydrogen radiates outside
the visible (in the infrared) portion of the spectrum, the thermal energy hazard from
a hydrogen fire will be less than from a natural gas fire of equivalent energy release
because of the absorption of thermal radiation by water vapor in the air. The lack
of a visible fire, however, can increase the hazard.
Heat is transmitted from a hydrogen fire to neighboring objects by thermal
radiation and convection. Factors affecting the thermal radiation intensity on an
object near a fire include:
the absorption of thermal radiation in the atmosphere between the flame
and the object
the temperature throughout the flame
the amount of soot in the flame (soot will not be produced by burning
hydrogen, but by burning of nearby materials)
the gas composition (in addition to a hydrogen/air mixture, a hydrogen and
natural gas/air mixture is also of interest)
An investigation is needed of the fire hazards or damage potential from hydrogen
fires considering these factors. Thermal radiation fluxes from hydrogen fireballs
and flames should be measured. Radiation to a point from a cloud combustion
should be studied.
Evaluation of the consequences of a hydrogen fireball (as a function of its size,
duration, and radiation) should be further developed for protection of personnel,
facilities, and equipment.

12.3.5. Overpressure Effects of Hydrogen Combustion


The overpressure developed from the unconfined combustion (both deflagra-
tion and detonation) of a hydrogen cloud should be investigated. Commonly, a
TNT-equivalent method is used to determine the overpressure from a hydrogen
fireball. This technique has some major drawbacks; for example, TNT produces a
short-duration, high-impulse pressure wave whereas a hydrogen fireball produces
a longer duration, lower impulse pressure wave. The external effects of the two can
be quite different; therefore, design for, or protection against, the overpressure
could be quite different in the two cases.

12.4. SLUSH-HYDROGEN SAFETY PROBLEMS

The properties ofliquid and slush hydrogen, especially slush hydrogen's very
low vapor pressure (below atmospheric), introduce a number of safety problems,
the most significant of which is the possibility of air in-leakage.
Safety Problems Needing Further Investigation 187

The problem of liquid or slush-hydrogen contamination with air may be


considered in four phases:
1. Detection of air contamination in liquid/slush hydrogen
2. Ignition of solid-air-liquid/slush-hydrogen mixtures
3. Confined combustion of a liquid/slush-hydrogen and air mixture
4. Response to detection of air contamination in liquid/slush hydrogen

12.4.1. Detection of Air Contamination in Liquid and Slush Hydrogen


The detection of air contamination in liquid or slush hydrogen presents a
difficult problem because of the possibility of the small quantity and nonuniform
distribution of the impurity. Thus, oxygen detection techniques present a significant
challenge. Sampling techniques that match the detection techniques also present a
significant challenge. In situ bulk measurements are preferable to localized sam-
pling and remote analysis.
There are several possible methods of analyzing for the presence of oxygen in
liquid or slush hydrogen, but none has been sufficiently developed. It is preferable
to obtain samples that are representative of the entire storage volume, given that a
solid-air impurity will not give any evidence of its existence, nor will it necessarily
be uniformly distributed within the hydrogen volume.
Although the objective is somewhat different, the sampling and analysis of
LNG has a number ofprocedures9,IO that are common to the sampling ofliquid or
slush hydrogen. In either case, the simplest method of analysis would be the
removal of a small sample from a larger volume of cryogenic fluid with the
consequent assumption that this sample is representative of the parent volume. The
LNG sample (a complex mixture) must be vaporized and warmed in such a manner
as to eliminate the possibility of composition fluctuations caused by selective
vaporization of the individual components (with various boiling-point tempera-
tures) and delivered to an analyzer (e.g., a gas chromatograph) of intrinsically high
sensitivity, accuracy, and precision. Also, all equipment and procedures must be
capable of operation under field, not laboratory, conditions.
An in situ sampling technique, especially with a rapid response, would be of
considerable advantage in detecting air contamination in either a storage vessel or
a transfer line. Obviously, this sampling would have to be done at temperatures
from 20 K (liquid) to 13.8 K (slush). Methods that could be considered include (1) a
measurement of opacity, (2) an analysis based on the paramagnetic properties of
oxygen, (3) neutron activation analysis, and (4) nuclear magnetic resonance (for
nitrogen). The use of any of these approaches will require that appropriate meth-
odology be developed.
A method for detecting and measuring air in-leakage into a liquid- or slush-
hydrogen system would be of considerable benefit.
188 Chapter 12

12.4.2. Ignition of Solid-Air-Hydrogen Mixtures


The safe upper limit of air contamination in liquid or slush hydrogen is
unknown, assuming that there is some level below which it cannot be ignited. What
concentration constitutes a dangerous quantity? Obviously, this level must be
detectable. Some considerations involved in ascertaining the concentration of solid
air in liquid or slush hydrogen that can undergo combustion include:
1. Distribution of the solid air within the hydrogen (dispersed versus concen-
trated)
2. Ignition method (such as electric discharge, shock wave, high-velocity
impact, metal fracture or tearing, and thermal input)
3. Energy input of the ignition source
4. Presence of inhibitors to a combustionreaction (such as helium ornitrogen)
There is some experience that can form the basis for the study of the ignition
of oxygen in liquid hydrogen. 11-13 This experience is largely centered on oxygen--
hydrogen mixtures having close to a stoichiometric composition. An extension of
this work is needed in which emphasis is placed on the hydrogen-rich limit to
combustion. However, the localized effect of an oxygen-hydrogen reaction could
actually be near stoichiometric concentration (another uncertainty that should be
examined). The suggested extension of previous studies should consider ignition
methods and the energy input required as well as what mechanisms might be present
in hydrogen systems to provide this energy (electric discharge, shock wave,
high-velocity impact, thermal inputs, etc.). Also, the study should determine the
effect of the distribution of the air within the hydrogen and the effect of combustion
inhibitors (does solid nitrogen inhibit ignition?). It should also examine whether
ignition leads to a deflagration or a detonation process.

12.4.3. Confined Combustion of a Slush-Hydrogen and Air Mixture


The energy release and the rate of reaction in a confined combustion as a
function of quantity, concentration, and dispersion of a mixture of slush hydrogen
and solid air must be determined. Usually, the energy release is presented as an
energy equivalent, such as grams of TNT per gram of mixture; however, the
characteristics of an energy release from an explosive such as TNT are quite
different from those from the reaction of a hydrogeIHlir mixture, and such an
equivalency may thus be inappropriate. The effects of inert gases, such as helium,
on energy release, rate of reaction, and combustion limits should be evaluated.
Such information is needed to permit evaluation of the response of contain-
ment structures to internal energy releases. The severity, and possible consequence,
of a combustion reaction can be evaluated, and this information would be valuable
in planning a proper response to the detection of air intrusion into a slush-hydrogen
Safety Problems Needing Further Investigation 189

container. The proper response may differ depending on the container's ability to
contain (confine) an energy release.

12.4.4. Response to Detection of Air Contamination in Liquid or Slush


Hydrogen
To determine the proper response to detection of air intrusion into a liquid- or
slush-hydrogen system requires safety judgment combined with information about
the items discussed above. Is the quantity of air above or below the level that can
be ignited? Will the vessel survive and contain a combustion if it occurs? An
immediate response to the detection of air contamination is probably desirable, but
some actions require longer to accomplish than others. How urgent a response is
required?
The response to the detection of an air impurity within a liquid- or slush-hy-
drogen system should depend upon the severity of the consequences ofan inadver-
tent combustion. Assuming that the result warrants an emergency reaction,
procedures to be considered include such actions as (1) immediate isolation from
energy sources (e.g., stirrers or electric power) and (2) flooding the system with
helium gas. (The effectiveness of the technique of flooding with nitrogen to inhibit
combustion is questionable.) A slower response (one that requires more time to
accomplish) is to allow the solid hydrogen in the slush to melt and then filter the
solid air from the liquid hydrogen. The filter could then be isolated and made inert,
and the air contamination removed from the system.
A safe way to make a slush-hydrogen system inert in an emergency is needed.
This should be based on proper modeling and experimental results that provide
confidence that the procedure will accomplish its intended goal.
Filtering has been considered as a method of slush replenishment by returning
triple-point liquid to the supply system with a replacement flow of slush hydrogen
being transferred to the storage vessel. In this case any accumulated solid air would
concentrate in the filter and remain in the system. Probably, the separation of solid
air is possible only after the solid-hydrogen portion of the slush has melted, leaving
liquid hydrogen containing the solid air particles at between 13.8 K and 20.27 K.
At this stage any air or other impurity except helium will still be a solid and can be
filtered. However, there is the possibility that the solid so collected will have a high
oxygen content, with the resulting problem of finding a safe method for the disposal
of the filtered solid fraction. A dual-filtering section on the return transfer line with
appropriate valving could allow alternate operation of the filters, thus providing for
periodic warm-up and analysis for contaminants. Techniques such as flooding the
isolated filter with an inert gas like nitrogen could be considered for inerting. Also,
an analysis of the gas within the isolated filter volume to determine the type of
contaminant trapped by the filter should be considered.
190 Chapter 12

Plans for dealing with possible air contamination in liquid or slush hydrogen
will require answers to questions such as:
Will solid oxygen or air transfer with liquid or slush hydrogen?
Does solid oxygen or air accumulate in one location in a tank, transfer line,
valve, etc.?
What is the impact sensitivity of a solid-oxygen particle hitting a filter
screen, pipe wall, valve, etc.?
What is the effect of entrainment for a high vent rate (such as burst disk
rupture) for a solid/liquid cryogen mixture?
Will solid-nitrogen or solid-oxygen particles plug relief valves,filters, etc.?
Do solid oxygen particles conglomerate, leading to contamination buildup,
or will they be distributed throughout the system?
Will hydrogen and oxygen gases mix or accumulate in layers if a contami-
nated system is warmed to above the NBP for oxygen or to room tempera-
ture?

12.4.5. Pressure Control


Pressure control is an essential requirement in a slush-hydrogen system. It is
very critical for lightweight flight systems. Factors affecting pressure control
include volume contraction/expansion upon freezing/melting and thermal stratifi-
cation in the slush hydrogen.
The technique of allowing thermal stratification to occur in a liquid layer above
slush hydrogen is based on experimental evidence generated, in large part, in
cylindrical storage vessels made of glass or stainless steel. In a storage vessel of
this type, stratification can be maintained. Ifundisturbed, the hydrogen will act as
an excellent insulator, and the stainless-steel container, with its low thermal
conductivity, will not have a great influence in decreasing the thermal gradient in
the fluid. If, on the other hand, vessels are fabricated of aluminum or copper, the
thermal transport up the vessel walls will increase by more than an order. of
magnitude. Thus, the experimental data for stratification may not be representative
of conditions that may exist in flight-type tankage in which lightweight materials,
such as aluminum, with its higher thermal conductivity, can decrease or destroy
thermal gradients. Because the pressure in a system containing slush hydrogen
depends upon the temperature of the vapor/liquid interface, the pressure control of
the system may be influenced by the thermal gradient in the tank wall. This effect
of material selection with high thermal conductivity is used to advantage in the
unvented transport of liquid helium. The same effect may be an advantage or a
disadvantage in the use of slush hydrogen, but it must be considered when selecting
hydrogen or helium as a pressurant for flight-weight or other tankage. In fact,
appropriate material selection might provide a means of passive pressure control
in slush-hydrogen storage. Consequently, the effects of storage vessel geometry and
Safety Problems Needing Further Investigation 191

materials of construction should be evaluated to determine how stratification is


affected.

12.4.6. Electric Charge Buildup


The possibility ofthe buildup of electric charge within liquid or slush hydrogen
is not in itself a hazard in the absence of oxygen. However, if air is present within
the system, such a charge buildup could be a likely source of ignition. Electric
charge buildup is a function of electrical conductivity and dielectric strength
parameters. Whether electric charge buildup is a problem is a function ofthe relative
rates of "charge accumulation" and "charge dissipation" within the flowing fluid.
Electric charge buildup is very small for flowing liquid hydrogen,14,15 but solid
particles in liquid hydrogen could greatly increase the buildup of an electric charge.
The type of particle (oxygen, nitrogen, hydrogen, sand, metal) could be important.
This subject has been studied for flowing liquid hydrogen. 14,15 These studies
indicate that for fluids with relatively high electrical conductivity (e.g.,
> 10- 10 n- I cm- I ) the conductivity of the fluid is sufficient to allow rapid dissipation
of any electric charge that would occur. At very low electrical conductivity (e.g.,
<10- 15 n- I cm- I ), a higher flow rate and longer time is required for accumulation
of any significant charge buildup, but charge dissipation is slow. Conductivities
intermediate between these limits can result in the buildup of significant charge
quantities and also restrict the dissipation of these charges. Hence, for pure
single-phase fluids, the greatest danger exists with fluids with intermediate electri-
cal conductivities.
The electrical conductivity ofliquid hydrogen has been measured 16 at about
10- n- I cm- I . Thus, liquid hydrogen is not among the liquids likely to experience
19
static electric charge buildup. However, the presence of solid particles or gas
bubbles within the flowing stream can greatly enhance a tendency to produce
electric charges. The presence of slush hydrogen ensures that there will be solid
particles within the flowing stream, and in the more hazardous situation where air
entrainment has occurred, the air will also be present as solid particles. In addition,
foreign particles such as sand and metal can greatly affect an electric charge buildup.
The possibility of electric charge buildup in a flowing cryogen stream with solid
particles needs investigation.

12.4.7. Long-Term and/or Large-Depth Storage


Aerospace applications require the long-term and large-scale storage of slush
hydrogen. These conditions may have an effect on the agglomeration of the solid
particles. The transfer of slush hydrogen under such conditions could involve a fluid
containing either snowflakes or snowballs (or both).
Aging studies for slush hydrogen have been performed with storage depths of
about 1 m (- 3 ft).17,18 However, the time involved has only been a few weeks. The
192 Chapter 12

storage of slush hydrogen with depths of at least S or 6 m (16-18 ft) should be


investigated. If any significant change in particle size, shape, or size distribution
results, then it will be necessary to reexamine the pumping characteristics of the
slush. The study should address the possibility of the solid particles of hydrogen
forming a large solid block upon aging (under different depth and pressure condi-
tions, for example).

12.5. QUANTITY-DISTANCE RELATIONSHIP FOR HYDROGEN


STORAGE

The most widely accepted quantity--distance (Q-D) recommendations for


gaseous and liquid hydrogen are NFPA SOA and NFPA SOB, issued by the National
Fire Protection Association (NFPA),19,20 but these do not address experimental
facilities nor do they consider slush hydrogen. The unique nature of facilities that
use slush hydrogen requires that the Q-D recommendations be reassessed.
The higher energy density of slush hydrogen compared to liquid hydrogen
might indicate a need for a more conservative Q-D relationship for slush hydrogen.
Subatmospheric pressure is involved; thus, there is a greater potential for air
contamination. A Q-D determination for a slush-hydrogen installation should also
include a consideration of the potential for air contamination and the hazards
associated therewith.
Obviously, site vulnerability will have a major impact on Q-D requirements,
as will the isolation of the site from other activities and facilities. If space is
available, one can be more conservative and use a greater separation distance than
that recommended in the standards.
A unified, consistent standard for gas, liquid, and slush hydrogen storage is
needed. The standard should address (1) the protection of a hydrogen system from
hazards associated with surrounding facilities and (2) protection of nearby person-
nel and facilities from the hazards associated with a hydrogen system. The standard
should include hazards such as blast (overpressure), shrapnel, thermal radiation,
fifes, and combustible cloud formation and dispersion as a function of quantity of
hydrogen stored.
The standard should also address the need for dikes, impoundments, and
barricades. One way to contain the spread of a liquid-hydrogen spill is to install
dikes around possible spill locations, such as around a liquid storage tank. A dike
will limit the spread of a liquid spill, but it may also limit the vaporization rate of
the spilled liquid hydrogen. For a particular installation or site, it may be important
to limit the vaporization rate to reduce the extent of the combustible cloud generated
as the result of a spill. However, it may also be important to maximize the
vaporization rate so that the spilled liquid hydrogen is vaporized and dispersed from
the spill site as rapidly as possible, regardless of the resulting combustible cloud
Safety Problems Needing Further Investigation 193

size. A standard is needed for the design, installation, and use of dikes around
liquid-hydrogen storage tanks. Such a standard should be based on an evaluation
of spill containment versus dispersion of a liquid-hydrogen spill. In some circum-
stances it may be preferable to channel a spill to a better place for disposal or to
have it burn there.
Another aspect of this standard should be consideration of the need for a water
cooling/deluge system for hydrogen storage systems, especially liquid and slush,
to keep the tank cool (not to put out afire); spraying of water on the vent system
must be prohibited (to avoid accumulating an ice blockage of the vent system).
Another consideration for inclusion in a hydrogen storage standard is the use
of hydrogen and flame detectors.
The standard should also address the need for protective clothing and safety
equipment for personnel. Conflicting guidelines exist regarding some personnel
protective clothing and equipment use. An example is whether or not ground straps
should be used on personnel working in the vicinity of hydrogen. Another is the
use of nonsparking tools in the vicinity of hydrogen, which some guidelines
recommend while others do not.

12.6. GUIDELINES, STANDARDS, AND REGULATIONS

A unified, consistent standard for the design, construction, operation, and


maintenance of cryogenic storage and piping systems is needed. The standard
should include the common cryogenic fluids; it should cover their gas, liquid, and
solid phases. The standard should address facility siting and construction and
facility design and layout (including proper quantity-distance requirements;
grounding; cleaning of components and systems; proper disposal of vented gases;
and proper provisions to preclude air contamination, such as double seals, guard
volumes, and helium pressurization). Specifications for recertification of a cryo-
genic piping or storage vessel that has been out of service should be included in the
standard. The standard should include personnel protection requirements. Neces-
sary risk analyses, design verifications, etc., should be addressed in the standard.
The cryogens could be separated into various categories, such as inert (nitrogen and
helium, for example), oxidizing (for example, oxygen and fluorine), and flammable
(hydrogen and LNG, for example).
An internationally accepted standard for cryogenic facilities, equipment, com-
ponents, and safety should be developed, especially for hydrogen systems.
One need not addressed in present standards for hydrogen storage is the
identification or markings that should be present to identify the facility. The exact
wording and the size of that wording should be specified.
The proposed safety standard for cryogenic facilities, equipment, and compo-
nents should address the design, fabrication, and testing of vacuum-insulated
194 Chapter 12

vessels. The inner container of a vacuum-insulated vessel can be coded and stamped
in accordance with the ASME Pressure Vessel Code. The ASME Pressure Vessel
Code addresses the thickness of the outer container of a vacuum-insulated vessel,
but some provisions of the code are not compatible with practices related to high
vacuum (such as double welding at penetrations because of the possibility of virtual
leaks), and others (such as pressure testing because of the need for external pressure)
can be difficult or expensive to achieve. Consequently, the outer container is usually
not code-stamped as is the inner container for a double-walled vessel. The proposed
standard should address the need for structural integrity and vacuum requirements,
inner tank loads on the outer tank, and external pressure testing. A greater pressure
loading of the outer tank could occur from a failure of the inner tank, and this might
dictate the design and testing requirement for the outer tank.

REFERENCES

1. Stewart, W. F., Dewart, J. M., and Edeskuty, F. 1. (1990). Safe venting of hydrogen, in Hydrogen
Energy Progress VIII (T. N. Veziroglu and P. K. Takahashi, eds.), Vol. 3, pp. 1209-1218, Pergamon
Press, Elmsford, New York.
2. Witcofski, R. D., and Chirivella, 1. E. (1984). Experimental and analytical analysis of the
mechanisms governing the dispersion of flammable clouds formed by liquid hydrogen spills, in
Proceedings of the World Hydrogen Energy Conference IV(T. N. Veziroglu, W. D. Van Vorst, and
1. H. Kelley, eds.), Pergamon Press, Elmsford, New York.
3. DeSteese, J. G., and Counts, C. J. (1982). Liquefied Gaseous Fuels Safety and Environmental
Control Assessment Program: Third Status Report, Battelle Pacific Northwest Laboratory, Report
PNL-4l72 UC.ll, Richland, Washington.
4. Dodge, B. F. (1944). Chemical Engineering Thermodynamics, McGraw-Hill, New York, pp.
297-298.
5. McCarty, R. D., Hord, J., and Roder, H. M. (1981). Selected Properties of Hydrogen, NBS
Monograph 168, U.S. Government Printing Office, Washington D.C.
6. Zabetakis, M. G. (\967). Safety with Cryogenic Fluids, Plenum Press, New York.
7. Stamps, D. w., Benedick, W. B., and Tieszen, S. R. (1991). Hydrogen-Air-Diluent Detonation
Study for Nuclear Reactor Safety Analyses, Sandia National Laboratories Report NUREG/CR-
5525, SAND89-2398, Albuquerque, New Mexico.
8. Sherman, M. P., Tirszen, S. R., and Benedick, W. B. (1989). Flame Facility, the Effect of Obstacles
and Transverse Venting on Flame Acceleration and Transition to Detonation for Hydrogen-Air
Mixtures at Large Scale, Sandia National Laboratories Report NUREG/CR-5275, SAND85-1264,
Albuquerque, New Mexico.
9. Parrish, W. R. (\985). Sampling and analysis, in LNG Measurement, A User's Manual for Custody
Transfer (D. B. Mann, ed.), Section 2.2, U.S. Department of Commerce, National Bureau of
Standards, NBSIR 85-3028, Boulder, Colorado.
10. Parrish, W. R., Arvidson, 1. M., and Labecque, L. R. (1978). Development and Evaluation of an
LNG Sampling Measurement System, U.S. National Bureau of Standards, NBSIR 85-3028,
Boulder, Colorado.
11. Lee, R. E. (1952). The Explosiveness of Solid Oxygen in Liquid Hydrogen, Cambridge Corp.
Technical Memorandum No. 19, Boulder, Colorado.
Safety Problems Needing Further Investigation 195

12. Cook, M. A., and Udy, 1. 1. (1962). Detonation Pressure of Liquid HydrogenlLiquid Oxygen,
Final Report for Contract No. NAS8-5058, George C. Marshall Space Flight Center, National
Aeronautics and Space Administration, Huntsville, Alabama.
13. Plaster, M., McClenagan, R., Phillips, M., Benz, F. J., and Ullian, 1. (1988). Detonation Properties
of Liquid Hydrogen and Liquid Oxygen, Proceedings of the 1988 JANAF Safety and Environ-
mental Subcommittee Meeting, Chemical Propulsion Information Agency Publication 485, Johns
Hopkins University Physics Laboratory, Laurel, Maryland.
14. Arthur D. Little, Inc. (1961). Final Report, Electrostatic Hazards Associated with the Transfer and
Storage of Liquid Hydrogen, Report to the Agena and Centaur Systems Office, Marshall Space
Flight Center, National Aeronautics and Space Administration, Huntsville, Alabama.
15. Cassutt, 1., Biron, D., and Vonnegut, B. (1962). Electrostatic hazards associated with the transfer
and storage of liquid hydrogen, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.),
Vol. 7, pp. 327-335, Plenum Press, New York.
16. Willis, W. 1. (1966). Electrical conductivity of some cryogenic fluids, Cryogenics 6 (October),
279.
17. Mann, D. B., Ludtke, P. R., Sindt, C. F., Cheiton, D. B., Daney, D. E., and Pollack, G. 1. (1965).
Characteristics of Liquid--Solid Mixtures of Hydrogen at the Triple Point, U.S. National Bureau
of Standards Report 8881, Boulder, Colorado.
18. Daney, D. E., and Mann, D. B. (1967). Quality Determination ofLiquid--Solid Hydrogen Mixtures,
U.S. National Bureau of Standards Report 9701, Boulder, Colorado.
19. National Fire Protection Association (1993). Standard for Gaseous Hydrogen Systems at Con-
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20. National Fire Protection Association (1993). Standard for Liquid Hydrogen Systems at Consumer
Sites, NFPA 50B, National Fire Protection Association, Quincy, Massachusetts.
Chapter 13

Accidents: Prevention and Examples

As mentioned in Chapter l, in order to have a safe operation, the system must be


both designed and constructed to be safe, and it must also be operated in a safe
manner. Safe operation requires excellent maintenance and housekeeping. Because
new and different applications of cryogenics are frequently encountered, the
possibility of inexperienced operators is always present. Furthermore, a new
application might entail usage that does not have any precedent or existing appli-
cable experience. Effective safety training is of the utmost importance, and the
operators must not only be well versed in the basis of cryogenic safety but also have
intimate knowledge of the system with which they are working. They must always
be aware of the total inventory of cryogens and also know the location and amount
of cryogen at every point in the system. Previous experiences, difficulties, failures,
and accidents provide valuable knowledge that is important to anyone involved in
the operation of a cryogenic system.

13.1. ACCIDENT PREVENTION BY DESIGN

A safe system design requires that safety be considered from the very begin-
ning of the design process. Once the design is under way, it is time to consider safety
reviews. One such review is a failure analysis of the system components [this is
commonly referred to as a failure modes and effects analysis (FMEA)]. These
components will probably have come from several different suppliers, and the
designer expects them to operate safely in concert with each other according to his
specifications. Under some circumstances, anyone of these components might fail
in a number of different ways. In the case of a valve, failure could result from such
actions as failing to open or close, opening further or less than commanded, leaking
through the seat or through the packing, or operating erratically.
The examination of the system design can be performed by personnel experi-
enced in safety, but this review should be performed together with the designers
and, if possible, also the operators of the proposed system. A more formal review
197
198 Chapter 13

system was devised in England l and is now followed in several other countries.
This system is referred to as the hazard and operability study, or HAZOP.
After an accident or operational difficulty, there is usually some kind of
investigation intended to prevent a recurrence and to allow as much as possible to
be learned from the incident. However, learning from experience is usually more
costly than would have been the case if the problem could have been anticipated.
Thus, the object of HAZOP is to create some "synthetic experience" or "20/20
foresight. "
The safety review of a cryogenic system is performed by a committee consist-
ing of a cryogenic engineer, a safety expert, a designer, a project manager, and other
technical advisers as required. Each component of the system is considered indi-
vidually, and then the system is treated as a unit. First, the purpose, function, and
performance of the individual unit is stated, and guiding questions are asked to
determine the possibility of failure of a given component. If vulnerabilities are
detected, remedies are determined, and the design or specifications can be modified.
In this way, either safety hazards can be eliminated or the consequences of a mishap
can be diminished.
In addition to the type of safety review represented by HAZOP, it will
frequently be necessary to present a safety analysis report to various authorities to
assure them of the safety of proposed new projects. Other safety review procedures
such as fault tree analysis and risk analysis are valuable investigative methods.

13.2. ACCIDENTS IN CRYOGENIC SYSTEMS

Although the history of cryogenic technology demonstrates an excellent safety


record, accidents have occurred. Unfortunately, with accidents that occur under less
common conditions, such as those involving the extremely low-temperature regime
of cryogenics, the unfamiliarity of the public with the situation frequently leads to
an inordinate fear of possible consequences. In one case, a minor fire, with no
serious consequences, occurred while a liquid-hydrogen transport trailer was being
unloaded and almost led to an (unnecessary) major evacuation of the surrounding
community. This is another case that demonstrates the necessity of emergency
personnel having safety training including proper response to emergencies involv-
ing cryogenic fluids.
Ordin has summarized NASA accidents involving the handling of liquid hydro-
gen. 2 His conclusion is that in the great preponderance of accidents the cause can be
traced to improper procedures or to failure to follow established procedures. Although
we do not know of any similar analysis of accidents with other cryogens, we believe
that, were such an analysis to be made, a similar conclusion could be drawn.
The following discussion of accidents does not represent a complete list of all
accidents involving cryogenics. Rather, it consists of examples of accidents about
Accidents: Prevention and Examples 199

which the authors have more than just a casual knowledge of the conditions or
causes.

13.2.1. Accidents with Hydrogen


The large-scale technology of liquid hydrogen has a history of about one-half
century. Therefore, although not as old as the similar technology ofliquid oxygen
and liquid nitrogen, it can be considered as a somewhat mature technology that will
probably see a further increase in size in the coming century.

13.2.1.1. Minor Explosions in a Hydrogen Vent System


In the initial design ofa facility handling large quantities [15,000 kg (56,000 gal-
lons)] of liquid hydrogen (LH2), all of the hydrogen vents were manifolded into a
common vent system terminating in a flare stack. At a time when no operation of
the system was in progress, but the liquid-hydrogen Dewars contained liquid
hydrogen and were venting the normal boil-off through the lighted flare stack, a
technician removed one of the check valves leading into the vent system from a
source other than the two Dewars. This subsystem did not contain any hydrogen at
the time. The removal of the valve created an opening through which air was
aspirated into the normal flow of hydrogen coming from the two liquid-hydrogen
Dewars. A few minutes later, there was an ignition of the hydrogen-air mixture that
had filled the vent system from the point of opening to its end, and the flame traveled
back to the point of the opening with a low audible noise and went out. After a
period of about 7 minutes, there was a second explosion, and this process was
repeated, over and over, at a regular interval of about every 7 minutes. An oxygen
monitor connected to the vent system near its exit showed that the explosions were
occurring when the oxygen concentration at the flare reached about 6%.
A technician closed the valves that were allowing the flow of hydrogen from
the Dewars. However, this act did not stop the explosions. The engineers correctly
assumed that the pressure pulse from the initial explosion had blown the rupture
disks backward toward the Dewars.
Each Dewar was equipped with a pressure relief valve and a rupture disk, in
parallel. Fortunately, in this case the rupture disk had been connected to the Dewar's
interior with a shutoff valve in between. (Such a design is no longer permissible).
This valve was locked in the open position. Therefore, the lock was opened, and
the valve closed. This action stopped the series of explosions.
There were no injuries. The only loss to the facility was the two rupture disks
and the remaining liquid hydrogen that was vented so that the Dewars could be
warmed up above 90 K to determine if any air had entered them during any back
flow that might have been caused by the explosions. Fortunately, this was not found
to have occurred. The rupture disks were replaced, and there were no further
consequences during the next decade of operation of the facility.
200 Chapter 13

A conclusion that can be drawn from this incident is that it is best not to join
separate components of a system to a common vent line when there is any
possibility of interaction. Also, with respect to the flaring of small flow rates of
venting hydrogen, this incident lends credence to the philosophy that says "if you
don't have a fire, why start one?"

13.2.1.2. Combustion of Hydrogen in the Open Atmosphere

An experiment was being performed to measure the sound level of a rapid flow
of hydrogen. 3 At the facility, the normal procedure was to flare any hydrogen release
greater than 0.45 kg/so The experiment was being performed in order to determine
the effect of the combustion on the acoustic field during the high-flow venting of
hydrogen. Therefore, one test was performed with flared hydrogen, and one with
unburned hydrogen.
The hydrogen entered the piping system connecting the hydrogen supply tanks
to the discharge nozzle at 23 MPa (3400 psi) and at ambient temperature. In the
case ofthe test with unburned hydrogen, the flow rate was ramped up to 55 kg/s in
13 s. That flow rate was maintained for lOs, and the flow was then ramped down.
After the flow had decreased to about 16 kg/s (in about 3 s), an unplanned ignition
occurred.
An attempt had been made to ensure the absence of ignition sources. The
hydrogen was obtained as liquid hydrogen and converted to high-pressure, ambient-
temperature gas in the storage bottles and was believed to be very pure. In addition,
the system had previously been blown down until there was no further evidence of
entrained solid particles in the effluent gas. However, it is very difficult to ensure
the absence of particulate matter in field-fabricated systems in a harsh climate.
Furthermore, the flow rates were higher than in the previous blow-down tests, and
it was estimated that the exit velocity of the hydrogen was in excess of 1200 mls.
It is believed that the ignition source was probably a static charge built up by
particulate matter in the exhaust stream or possibly a particle striking a solid object
near its discharge. One other possible ignition source could have been the rupture
of a metal rod that was supporting some instrumentation. The rod was found to be
broken after the explosion.
At the time of the ignition, approximately 900 kg (1980 lb) of hydrogen had
been vented, and it was estimated that about 10% of this amount participated in the
combustion. The closest observers, located in the open about 800 m (2625 ft) away,
did not detect a pressure wave. However, windows were rattled in a building about
3200 m (2 mi) away.
In the closer buildings, there was some superficial damage. In the concrete test
cell, a door latch was broken, and two plate glass windows were also broken. This
was at a distance of about 20 m (66 ft) from the exit ofthe nozzle. At a distance of
about 35m (115 ft), a laboratory mill-type building suffered a cracked window and
Accidents: Prevention and Examples 201

some slight bending of one of its structural members, but the damage was not
sufficient to warrant any repair. From the extent of the damage, it was estimated
that the buildings had experienced an overpressure of 1.2-2.4 kPa (0.17-0.34 psi).
Motion pictures of the explosion had been taken. These were color pictures
taken at 100 frames per second and infrared pictures taken at 96 frames per second.
From these pictures it was possible to observe that the flame front was traveling at
30 mls. This velocity is of interest because it is an order of magnitude higher than
what would have been expected from a deflagration, but almost two orders of
magnitude lower than that of a detonation.
From this incident it can be concluded that it is very difficult to eliminate all
ignition sources from rapidly venting hydrogen. Also, the experiment lends support
to the opinion that only a small part of the total amount of vented hydrogen actually
participates in a combustion like this (10% in this case). Another observation was
that the deflagration flame-front velocity can be significantly accelerated to reach
a velocity an order of magnitude higher than that of a simple deflagration, but more
than an order of magnitude lower than that of a detonation.

13.2.1.3. Liquid Hydrogen Storage Dewar Explosion

An LH2 storage Dewar used to supply gaseous hydrogen (GH2), through a


vaporizer, to a semiconductor fabrication building exploded, causing property
damage and injury to five persons in the vicinity of the Dewar. The Dewar had a
capacity of 34 m 3 (9000 gallons) and a working pressure of 1.03 MPa (150 psi).
All vent piping from the Dewar was connected to a single vent stack located near
the northeast comer of the tank and extended well above the tank. The Dewar was
leased from a LH2 supplier and was installed about 45.7 m (150 ft) from the facility's
main building. The Dewar had been in operation approximately three months before
the explosion occurred.
The significant events involved in the explosion include the following. The
Dewar was filled on a Thursday, and on Friday it was inspected by the LH2 supplier,
who found that conditions were normal. On Saturday at 12:05 P.M. a fire was reported
on the control end of the Dewar. City fire fighters sprayed that end of the Dewar
with water for cooling. Company officials and the LH2 supplier were notified of
the fire at 2:00 P.M. A plant engineer closed the valves to cut off the hydrogen (H2)
flow to the facility, and the fire was out at 4:50 P.M. The tank was cool to the touch
at 5:00 P.M. The following damage was noted at this time: a portion of the outer shell
at the lower north end was dished in, all gauges were damaged, the valves and
fittings showed evidence of heating, and piping sagged to the ground. The top
portion of the vent stack was bent toward the ground. The bent portion was
removed, leaving the stack much shorter than before.
At 7:00 P.M. personnel from the plant and the LH2 supplier started injecting
gaseous nitrogen (GN2) into the LH2 tank to boil away LH2. The damaged pressure
202 Chapter 13

gauge on the tank was replaced with a new 200-psi gauge (one report indicated that
it had a much higher range). This gauge indicated zero tank pressure. Some
witnesses stated that the tank was venting through a blown rupture disk and that
there was a slight leak from the vaporizer inlet valve.
Conditions were stable and all personnel left at 9:00 P.M. However, several
people visited the site during the night and reported that conditions were satisfactory
and that there was a frost buildup on the outside of the vent pipe and around the
vaporizer inlet valve, both indicating continued venting of the H 2.
At 8:30 A.M. on Sunday, the insulation vacuum was 46.7 Pa (0.35 Torr). At 9:30
A.M., the N2 injection was stopped. To speed up H2 vaporization, the vacuutn valve
was opened slightly at 10:30 A.M. and fully opened at 11 :30 A.M. Some increase in
venting rate and frost buildup on the stack was noted, but still no reading showed
on the new tank-pressure gauge. Six witnesses were present; as conditions appeared
to be stable, all personnel left the immediate vicinity of the Dewar at 11 :54 A.M.
They were ready to enter their cars in the parking lot on the other side of a
2.4-m-high (8-ft-high) chain link fence about 15.2 m (50 ft) from the Dewar when
the Dewar exploded at 11 :58 A.M. The explosion was heard and the flame was seen
a mile away. The city fire department arrived at 12:05 P.M. and wet down the area,
although the fire seemed to be out 3-4 minutes after the explosion.
The only people near the explosion were the six in the parking lot. One of these
was not injured, but five had skin burns (some third degree), shrapnel wounds, and
blast effect wounds (punctured ear drums and impact with ground----one reported
being "scooted" across several feet of pavement). None of the injuries was serious.
The Dewar was extensively damaged. Both the inner and outer shells ofthe Dewar
were split into numerous pieces and scattered around the area. Some large pieces were
found several hundred feet from the Dewar site. AO.3 m x 0.3 m (1 ft x 1 ft) piece was
found at 366 m (1200 ft), and a piece of the aluminum inner shell, 1.5 m (5 ft) in
diameter and weighing about 86.4 kg (190 lb), was at 91.4 m (300 ft). At 45.7 m
(150 ft), the nearest wall of the main building was pushed in. All windows were
broken, and the interior furnishings were scattered ("as if a tornado had hit").
Another building about 305 m (1000 ft) away had minor damage.
The fuel source for the original fire on Saturday could have been a leaking
compression fitting in the control area of the Dewar or the vent stack drain line.
The cause of the explosion on Sunday was attributed to an Hr02 reaction by one
person, who mentioned some possible sources of contamination. However, the
dominant feeling was that breaking the vacuum was the cause of the explosion.
Exactly what happened is uncertain, but it was speculated that a partial blockage
in the vent line prevented adequate venting of the high boil-off rate after the
insulation vacuum was broken, and the resulting pressure buildup in the tank caused
its rupture. The blockage in the vent system was postulated to possibly be from
either (1) impurities in the tank contents, (2) water sprayed on the tank after the
fire, (3) water condensed from the atmosphere following the removal of the section
Accidents: Prevention and Examples 203

of the vent pipe, or (4) the nitrogen purge placed on the tank. The accident analysis
indicates that the partial blockage apparently in existence up until Sunday morning
was not so severe as to prevent the escape of reasonable amounts of hydrogen that
are normally vented. However, the remaining vent area was not adequate to handle
the increased boil-off resulting from breaking the vacuum in the insulation space.
It is also speculated that there was a blockage to the tank pressure gauge so that it
did not indicate the actual tank pressure.
Some conclusions from this accident include: (1) redundant instrumentation
is recommended to provide an adequate, and believable, indication of actual
operating conditions; (2) more than one vent point should be provided because the
failure of a single vent could result in damage to the equipment and injury to
personnel; (3) advance emergency planning should address appropriate actions to
be taken in the event of possible emergency conditions; and (4) no action should
be taken until the total consequences ofthat action have been thoroughly evaluated.

13.2.2. Accidents with Liquid Nitrogen


13.2.2.1. Laboratory Dewar Explosion during Transfer of Liquid Nitrogen
During an attempt to transfer liquid nitrogen from a 160-L supply cylinder to
a 50-L laboratory Dewar, an improper and dangerous hookup was tried. The 160-L
Dewar was of the more recent style, being insulated with evacuated multilayer
thermal insulation and having a liquid discharge connection that had to be mated
with a flexible metal transfer line connected to the Dewar with mating screw
threads. The other end of this line is intended to be mated by screw threads to a
similar connection on the receiving Dewar, which also has two openings, one for
the fill tube and the other for a vent tube to exhaust the boil-off vapors during the
transfer of the liquid.
The receiving Dewar was of an old style, consisting of an internal50-L storage
sphere with only one pipe for both vent and fill and insulated with a spherical
vacuumjacket. This latter Dewar is intended to be filled by connecting a metal tube
(about 6 mm outside diameter and frequently called a wand) to a flexible tube (often
a piece of rubber tubing) and inserting the loose-fitting metal tube into the opening
of the Dewar (about 14 mm inside diameter). The other end of the flexible tube is
then connected to the supply Dewar, and the transfer is made with the boil-off
vapors and previous nitrogen atmosphere exiting the 50-L Dewar in the annular
space between the wand and Dewar fill tube. This method has been used for many
decades and works safely when done properly.
When the attempt was made to fill the receiving Dewar from the supply
cylinder, it was found that the two different fill tubes were not compatible. The
metal tube was too large to enter the 50-L Dewar, and there was no other way to
connect to the discharge port of the 160-L supply cylinder. Therefore, a large
thick-wall rubber tube was found that could be pushed over the end of the metal
204 Chapter 13

transfer tube and also pushed over the open end of the 50-L Dewar (with great
difficulty). A schematic of the setup is shown in Fig. 13.1a.
It was realized that with this arrangement there was no vent for the transfer
process, so a notch was cut in the end of the rubber tube where it was pushed over
the end of the metal transfer tube. It is doubtful whether this expedient could have
been very effective in that gas would have to flow in the opposite direction to the
liquid flow in a fairly small tube. However, the vent was further compromised by
pushing the metal tube so far into the rubber tube that the notch was closed off.

Metal Transfer Line

Transfer
Line
Rubber
Hose

l60-Liter
Dewar

50-Liter
Dewar
Dolly

Fig. 13.1a. Schematic of liquid-nitrogen transfer arrangement.


Accidents: Prevention and Examples 205

The transfer was then started and had proceeded for about 15 minutes when a
loud "pop" was heard. The transfer was stopped by closing the valve on the supply
cylinder, and the two workers took cover. After about two minutes there was no
further sign of anything wrong, so one of the workers tried to remove the rubber
hose. The hose was now very stiff and could not be removed, so one of the workers
started to open the threaded connection on the supply cylinder with a wrench and
was in the process of doing so when the 50-L Dewar exploded. He was seriously
injured, and there was an undetermined amount of damage to the laboratory.
Upon further inspection, it was learned that the supply cylinder had a higher
pressure rating than had been thought. The workers thought that they were working
with a vessel at a gauge pressure of about 160 kPa [23 psi] (gauge), but the vessel
was actually operating at 1.58 MPa [230 psi] (gauge). Therefore, it was initially
believed that the higher pressure in the supply cylinder was what caused the
explosion.
However, upon further examination, this was found to be a questionable
assumption. First, three sets of calculations were made independently, two after the
accident and one made and then tested experimentally by the Dewar's manufacturer
in the 1960s.4 These calculations all indicated gauge burst pressures in the vicinity
of2.07 MPa [300 psi] (gauge), a pressure greater than any pressure available from
the supply cylinder. Second, it was estimated that during the 15-minute transfer
period about 45 L would have been transferred into the 50-L Dewar. At this point
the pressure in the supply cylinder would have decreased to about 1.24 MPa
[180 psi] (gauge), and the pressure in the 50-L Dewar would have risen to be almost
as great. When liquid is withdrawn from a cryogenic Dewar containing saturated
liquid under pressure, the remaining pressure in the Dewar can be calculated from
the first law ofthermodynamics. 5 In order to prove this point, a withdrawal test was
made using a similar Dewar, and this test verified the calculations.
An important consideration in reaching an understanding of the mechanism of
the accident is that the method of filling subjected the 50-L Dewar fill tube to a
different cooling mechanism than ordinarily would have been the case if the wand
had been used in the usual manner. When a Dewar is filled with the wand loosely
inserted in the fill tube, the cold liquid does not touch the fill tube directly. The
wand usually penetrates into the Dewar below the end ofthe fill tube, and the liquid
drops directly to the bottom of the storage sphere after it leaves the end of the wand.
Thus, the only cooling that the fill tube experiences is from the boil-off gas with
lower heat capacity and also a lower heat-transfer capability. With the fill method
used in this accident, the liquid could flow directly on the tube wall and cool it
faster. A computation of the heat transfer in this process showed that not only the
fill tube could be cooled, but also the brass spacers that fastened the outer vacuum
jacket to the top of the fill tube and, in addition, the upper cylindrical part of the
vacuum jacket around the fill tube would also be cooled. With a heat-transfer rate
of 14 W, about 10 minutes of this cooling is sufficient to cool the upper vacuum
206 Chapter 13

jacket tube to about 150 K. The outer sphere that is joined to this tube, on the other
hand, presents a much larger surface to the outside temperature, and for it to receive
the same rate of heat transfer from the external atmosphere, its temperature would
only have to drop about 4 K. Consequently, the upper tube of the vacuum jacket
can be cooled much more than the outer spherical part of the vacuumjacket. Thus,
there can exist a sharp temperature gradient across the joint between the outer
sphere and its junction with the upper tubular part of the vacuum jacket (see Fig.
13.1b). This temperature difference was shown to be adequate to break open the

nner Necktube
(Stainless Steel)

Outer Necktube
(Copper)

Joint B

Outer Vacuum Container Inner Liquid Container


(Copper) (Copper)

Fig. 13.1b. Detail of the top ofthe 50-I Dewar shown in Fig. 13.1a.
Accidents: Prevention and Examples 207

solder joint at this junction and allow the atmosphere to enter the vacuum jacket.
Examination of the pieces of the ruptured Dewar showed a wide crack, opening
almost halfway (about 160) around this joint (joint B in Fig. 13.lb).
The normal boil-off loss of the Dewar was computed to be a little over 5.1 %
per day, equivalent to a heat input of2. 7 W. The loss was later measured on a similar
Dewar and found to be 5%. Breaking the vacuum can be calculated to increase this
loss rate by a factor of about 75, to over 200 W. If the Dewar were filled to 45 L,
this heat input can raise the Dewar pressure at the rate of 4 70 kPa ( 68 psi) per minute.
Thus, if the "pop" was indeed the cracking open of the joint in the vacuum jacket,
a period of about two minutes would be expected to be what would be needed to
raise the pressure of the 50-L Dewar to its bursting pressure. Of course, even if the
vacuum jacket had not been opened to the atmosphere, the normal heat leak would
eventually have raised the pressure to the bursting point, but that would have taken
over two hours.
If the initial "pop" had been the opening of a leak in the inner shell, the liquid
rushing into the warm vacuum jacket would be expected to raise the system to
bursting pressure much more quickly than in two minutes.
This accident is another example of the danger of quick fixes without proper
planning and without consideration of the possible consequences. Makeshift ar-
rangements should not be attempted, and training in working with cryogenic fluids
should stress the potential danger of the buildup of pressure, which, in some
circumstances, can be too rapid to permit remedial action to be taken.

13.2.2.2. Laboratory Dewar Explosion during Storage of Liquid Nitrogen


A laboratory worker, inexperienced in cryogenic techniques, was attempting
to extend the holding time of an experiment being cooled with a small liquid-
nitrogen Dewar (about 2 L in volume). He located a 30-L Dewar and made a top
closure from an aluminum plate fastened to a thick-wall aluminum tube about 8 em
in diameter and 8 cm long. This top closure was then fitted to the top of the Dewar
after installing in it two tubes, one to drain the liquid into the small Dewar and the
other to serve as the vent from the 30-L Dewar. He had mistakenly assumed that
the vent was to allow air to enter the Dewar to replace the liquid nitrogen that had
drained out. He had not realized that the aluminum closure added about 250 cm2
of heat-transfer surface directly exposed to the ambient temperature of the room.
With the Dewar inverted to feed directly into the smaller Dewar, the liquid nitrogen
was constantly in direct contact with the aluminum plate and tube; therefore,
nitrogen gas was constantly being evolved by heat transfer from the aluminum
closure. Thus, the vent was needed to relieve the pressure that otherwise would
have been built up in the Dewar by the evaporating nitrogen.
The Dewars were both filled and connected, and the experimenter left the
laboratory. About a half-hour later there was an explosion. The 30-L Dewar was
208 Chapter 13

destroyed, and there was some superficial damage to the laboratory. Fortunately,
there was no one in the room when the explosion occurred.
Calculations showed that the vent should have been adequate, even for the
very high venting rate that occurred. A subsequent examination of the vent pipe
showed that a foreign object had been inserted into the end of the vent pipe, probably
a screw because there was evidence of the remains ofa screw thread in the inside
of the end of the vent pipe. While no explanation was forthcoming as to the reason
for this action, it is suspected that the high rate of venting was sufficiently noisy to
disturb some other worker who thought that he/she could suppress the noise by
inserting a relatively tight-fitting screw into the end of the vent tube. However, the
guilty party could not be found.
This accident illustrates the fact that quick fixes seldom work and are fre-
quently dangerous. Also, the importance of adequate training is obvious, as such
training would have shown the first experimenter that his plan would not work, and
the second person would have realized how dangerous his or her action was.

13.2.3. Accident with Liquid Helium


During the transport of a 100-L Dewar by air, it was necessary to transfer the
Dewar between planes en route. The transfer of the Dewar from one aircraft to the
other was being attempted with a forklift. The Dewar fell off the forklift and landed
in such a way that the vent tubes on the top of the Dewar were bent and partially
blocked. The Dewar was an old-style Dewar with a liquid-nitrogen jacket, so that
two cryogens were involved. The hissing of the vent tubes alanned the airport
personnel. The Dewar was taken to a remote area of the airport. At what was
considered a safe distance, a hole was shot in the Dewar by a marksman. After some
additional hissing discharge of venting gas through the bullet hole for about five
seconds, the Dewar violently ruptured, propelling the upper half of the Dewar
rapidly to a height of several hundred feet. No injury or damage occurred other than
to the Dewar.
The accident demonstrates that a Dewar with two vents is safer. Also, the newer
Dewars have a protective ring above the vent system which would probably have
kept the vent tubes from being bent. In any case, carrying the Dewar on a raised
forklift and not having it secured so that it cannot fall is not good safety practice.
Because the ruptured Dewar pieces went straight up and came down close to the
same place, there were no injuries. This might have been a fortuitous occurrence,
and in another instance such an accident might have been more hazardous.

13.2.4. Accident with Liquid Oxygen


During the flightto the moon ofApollo 13, there was an explosion of an oxygen
tank that was supplying oxygen to the fuel cells and also breathing oxygen for the
astronauts. The accident was caused by a series of events that started with a
Accidents: Prevention and Examples 209

technician installing an extra bolt that was to hold the oxygen tank's supporting
segment to the frame of the service module during initial assembly at the contrac-
tor's plant where the service module was being assembled. A second technician did
not know that an extra bolt had been installed, and when he went to remove the
segment with the oxygen tank in place, he removed the bolts that he was aware of
but left the extra bolt still attaching the segment to the frame of the service module.
The crane that was used to lift the segment was not strong enough because of the
extra load of the weight of the segment as well as the resistance of the still-attached
bolt, and the crane broke, allowing the segment to fall back a few inches onto its
mounting.
The design of the oxygen tank included a short insert piece of aluminum tubing
to connect the upper part of the fill tube to the lower, slightly offset part of the fill
tube. The short piece of aluminum tube was joined to the other parts of the tube at
both ends by Teflon bushings (sleeves). Although the vessel could be filled without
a tight connection at this point, a tight connection to the lower tube was needed to
empty the liquid during the detanking procedure that would be required later.
Unknown at that time was the fact that if all tolerances were at their limit, the
aluminum tube with its Teflon sleeves would just barely span the distance between
the two tubes it was to connect (see Fig. 13.2). The jarring caused by the service
module segment falling back onto its support was able to dislodge the plastic insert,
in effect opening a hole in the discharge path, similar to a hole in a drinking straw.
However, there was no external evidence of this occurrence. The service module
was sent to Cape Kennedy for installation in the Apollo 13 vehicle.
Before launch the checkout procedure called for a filling of the oxygen tank
to ensure that it was in working condition. After the tank was confirmed to be
holding the liquid oxygen satisfactorily, it was to be detanked to await its final filling
before launch. However, when the detanking was attempted, no liquid could be
discharged through the fill tube by the application of pressure through the tank's
vent tube. Therefore, it was decided to use an alternate procedure of turning on a
heater within the tank and allowing it to evaporate the liquid oxygen. This was felt
safe to do because ofa thermal cutoff switch that would turn off the tank's internal
heater ifthe temperature were to rise too high. The heater was turned on and allowed
to heat the tank's interior over the following weekend. On Monday morning the
liquid had all been removed.
The oxygen supply to the fuel cells was designed to supply oxygen at about
6.9 MPa (1000 psi). This pressure would be maintained by the tank's internal heater,
and a uniform internal temperature would be ensured by a small fan within the tank.
This fan could be turned on to stir the fluid when the heater was operated. Thus,
with the operation of the heater and the fan, there would be a constant supply of
high-pressure oxygen. The 6.9-MPa (1000 psi) pressure is .above the critical
pressure of oxygen (see Table 1.1) so that no vaporization is involved in the
operation of the tank, and the density of the contained oxygen merely decreases as
.......
<::>

Fill Vent Feed


Line Line Line

ilter

'... Sleeve
(Teflon)
L....J...L....JII Gauging Probe
(Aluminum)

Standpipe
n
=-
~
~
...
....
Fig. 13.2. Schematic of the oxygen tank that caused the explosion in Apollo 13. ...
Accidents: Prevention and Examples 211

the supply is used, with the maximum withdrawal of oxygen being reached when
the maximum allowed temperature is attained.
Subsequent testing of a similar thermal cutoff switch showed that the thermal
cutoff feature failed upon continued heating, allowing the heating current to persist
during the entire heating period over the weekend. The excessively high tempera-
ture attained was shown to bake the Teflon insulation on the heater and fan wiring
until it cracked and some pieces fell off. When the Apollo 13 was launched, placed
into the holding orbit, and then launched on the flight path to the moon, glitches in
the electrical system began to appear. Eventually, there was a pressure excursion
above the intended 6.9-MPa (1000 psi) level, and there was an explosion, blowing
off the cover of the service module where the oxygen tank was located. The
departure of the cover damaged one of the antennae and momentarily disrupted
communications with the ground. Also, the pressure in the oxygen tank decayed
rapidly to zero. Fortunately, the astronauts were rescued and returned to earth safely.
Subsequent investigation by an examining panel (including one of the authors,
FJE) showed that the electrical shorting had ignited the Teflon insulation, which
was shown to be capable of fairly rapid combustion in the high-pressure oxygen
atmosphere. Most of the combustion took place in the tube that served as the electric
wire feed-through into the Dewar's interior. The heating weakened the tube until it
ruptured, blowing off the top cap of the Dewar and causing the previously
mentioned occurrences and discharging the oxygen to the vacuum of space. This
analysis led to the conclusion that the main body of the tank was probably still
intact.
As the service module was jettisoned before reentry into the Earth's atmos-
phere, one of the astronauts was able to take a photograph of it as it floated off into
space. Unfortunately, the photograph was very seriously back-lighted by the sun,
and only a black area was visible where the tank was supposed to be. However, a
computer enhancement of the photograph was done, and the photograph then
showed that the tank was indeed there, and still intact.
Although such an accident might never have been thought possible because
so many anomalies were required to occur in sequence, this was a case where
several mishaps all occurred in series, leading to the accident. It should be pointed
out that the explanation of the accident might not have been possible were it not
for the excellent records that were kept by NASA. Another contributing factor was
the excellent support that was given to the analysis team in the way of performing
verification experiments when requested. In particular, this included the testing of
the duplicate thermal cutoff switch to show that it would fuse in the closed position,
the photographing of Teflon burning in high-pressure oxygen, and the computer
enhancing of the last photograph of the service module as it floated off into space.
The importance of record keeping cannot be overemphasized if one is to learn from
mishaps and prevent their recurrence.
212 Chapter 13

13.3. CONCLUSION

Notice that most of the accidents described in this chapter involve actions by
operating personnel that, in retrospect, seem inappropriate and stem from inade-
quate knowledge of the consequences of these actions. These accidents emphasize
the need for adequate and continued training.

REFERENCES
1. Knowlton, R E. (1981). Hazard and Operability Studies, Chemetics International Ltd., Vancouver,
Canada.
2. Ordin, P. M. (1974). Review of hydrogen accidents and incidents in NASA operations, in
Proceedings of the Ninth Intersociety Energy Conversion Engineering Conference, pp. 442-453,
American Society of Mechanical Engineering, New York.
3. Reider, R, Otway, H. J., and Knight, H. T. (1965). An unconfined, large-volume hydrogen/air
explosion, Pyrodynamics 2, 249.
4. Scott, L. E. (1964). Neck plug experiments in liquid-helium shipment, in Advances in Cryogenic
Engineering (K. D. Timmerhaus, ed.), Vol. 9, pp. 379-389, Plenum Press, New York.
5. Van Wylen, G. J., and Sonntag, R E. (1986). Fundamentals of Classical Thermodynamics, John
Wiley & Sons, New York.
Appendix A

Some Pertinent Details of the Code of


Federal Regulations

A listing of the elements of the Code of Federal regulations that are pertinent to the
handling of cryogenic fluids is given in Table 11.12. Further details of these
elements are presented in this Appendix. Table A.l gives additional details of some
of the regulations pertaining to liquefied natural gas facilities. Table A.2 presents a
similar listing for cryogenic liquid tank car tanks, and Table A.3 gives further details
of OSHA regulations for the handling of cryogenic liquids in the work place.

Table A.I. Liquefied Natural Gas Facilities: Federal Safety Standards (49 CFR Part 193)

SubpartA--{Ieneral
Section 193.1 Scope of part
193.3 Applicability
193.5 Definitions
193.7 Rules of regulatory construction
193.9 Filing inspection and maintenance plans
193.11 Incorporation by reference
Subpart B-Site Related Design Requirements
Section 193.101 Scope
193.\03 Acceptable site
193.107 Thermal radiation protection
193.109 Combustible vapor-gas dispersion protection
193.111 Seismic investigation and design
193.113 Flooding
193.115 Soil characteristics
193.117 Wind forces
193.119 Other severe weather and natural conditions
193.121 Adjacent activities
193.123 Separation of components
Subpart C-Materials
Section 193.201 Scope
193.203 General
193.205 Extreme temperatures; normal operations
213
214 Appendix A

193.207 Extreme temperatures; emergency operations


193.209 Insulation
193.211 Cold boxes
193.213 Piping
193.215 Concrete materials subject to LNG temperatures
193.217 Combustible materials
193.219 Records
Subpart D-Design ojComponents
Section 193.301 Scope
193.303 General
193.305 Valves
193.307 Piping, general
193.309 Pipe supports
193.311 Buildings, design
193.313 Buildings, ventilation
193.315 Low temperature
193.317 Expansion and contraction
193.319 Frost heave
193.321 Ice and snow
193.323 Electrical systems
193.325 Lightning
193.327 Boilers
193.329 Combustion engines and gas turbines
Subpart E-Impoundment Design and Capacity
Section 193.401 Scope
193.403 Impoundment required
193.405 General design characteristics
193.407 Classes of impounding systems
193.409 Structural requirements
193.411 Impounding surfaces
193.413 Floors
193.415 Dikes, general
193.417 Vapor barriers
193.419 Dike dimensions
193.421 Covered systems
193.423 Gas leak detection
193.425 Inerting systems
193.427 Sump basins
193.429 Spill removal
193.431 Water removal
193.433 Shared impoundment
193.435 Other components and materials
193.437 Impoundment capacity; general
193.439 Impoundment capacity; storage tanks
193.441 Impoundment capacity; equipment and transfer facilities
193.443 Impoundment capacity; parking areas; portable containers
193.445 Flow capacity in Class 3 impounding systems
193.447 Sump basin capacity
Subpart F-Storage Tanks
Section 193.501 Scope
193.503 General
Code of Federal Regulations 215

193.505 Loading forces


193.507 Stratification
193.509 Movement and stress
193.511 Penetrations
193.513 Overpressure
193.515 Underpressure
193.517 External temperature
193.519 Internal temperature
193.521 Foundation
193.523 Frost heave
193.525 Insulation
193.527 Instrumentation for storage tanks
193.529 Metal shells and containers
193.531 Concrete shells and containers
193.533 Thermal barriers
193.535 Support systems
193.537 Internal piping
193.539 Marking
Subpart G-Design of Transfer Systems
System 193.601 Scope
193.603 General
193.605 Shutdown control system
193.607 Backflow
193.609 Overfilling
193.611 Cargo transfer systems
193.613 Marine transfer
193.615 Tank car and tank truck transfer
193.617 Emergency valve
Subpart H-Gasification Equipment
Section 193.701 Scope
193.703 General
193.705 Fired gasifiers
193.707 Downstream pressure
193.709 Downstream temperature
193.711 Operational control
193.713 Shutoff val ves
193.715 Relief valves
193.717 Warning devices
193.719 Combustion air intakes
Subpart I-Liquefaction Equipment
Section 193.801 Scope
193.803 General
193.805 Control of incoming gas
193.807 Contaminants
193.809 Reverse flow
193.811 Cold boxes
193.813 Air in gas
193.815 Equipment supports
Subpart J-Controi Systems
Section 193.901 Scope
193.903 General
216 Appendix A

193.905 Relief devices


193.907 Vents
193.909 Sensing devices
193.911 Warning devices
193.913 Discharge pressures and temperatures
193.915 Pump and compressor control
193.917 Control valves
193.919 Shutdown control systems
193.921 Control center
193.923 Auxiliary controls
193.925 Failsafe control
193.927 Sources of electrical power
Subpart K-Construction
Section 193.1001 Scope
193.1 003 General
193.1 005 Construction procedures
193.1007 Identification of critical processes
193.1009 Qualification of construction personnel
193.1011 Construction inspection
193.1013 Qualification of inspectors
193.1015 Cleanup
193.1017 Pipe welding
193.1019 Piping connections
193.1021 Testing acceptance
193.1 023 Testing, general
193.1025 Strength tests
193.1027 Nondestructive tests
193.1029 Leak tests
193.1031 Testing control systems
193.1033 Storage tank tests
193.1035 Inspection of materials
193.1037 Construction records
Subpart ~perations
Section 193.1101 Scope
193.1103 General
193.1105 Operating procedures
193.1107 Monitoring operations
193.1109 Emergency procedures
193.1111 Personnel safety
193.1113 Personnel participation
193.1115 Training
193.1117 Transfer procedures
193.11l9 Protective transfer operations
193.1121 Investigation of failures
193.1123 Security; procedures and personnel
193.1125 Security; enclosures required
193.1127 Security; enclosure design
193.1129 Security; enclosure accesses
193.1131 Security; lighting
193.1133 Security; monitoring
193.1135 Security; warning signs
193.1137 Maximum allowable operating pressure
Code of Federal Regulations 217

193.1139 Purging
193.1141 Operating records
Subpart ~Maintenance
Section 193.1201 Scope
193.1203 General
193.1205 Maintenance procedures
193.1207 Maintenance of fire fighting equipment
193.1209 Isolating and purging
193.1211 Testing repairs
193.1213 Contaminants
193.1215 Testing control systems
193.1217 Testing transfer hoses
193.1219 Inspecting storage tanks
193.1221 Maintenance records
Subpart N-Fire Prevention
Section 193.1301 Scope
193.1303 General
193.1305 Fire prevention plan
193.1307 Fire fighting plan
193.1309 Coordination with public safety agencies
193.1311 Training
193.1313 Records
Subpart O-Corrosion Control
Section 193.1401 Scope
193.1403 General
193.1405 Corrosion control overview
193.1407 Atmospheric corrosion control
193.1409 External corrosion control; buried or submerged components
193.1411 Internal corrosion
193.1413 Environmentally induced cracking
193.1415 Interference currents
193.1417 Contaminants
193.1419 Monitoring corrosion control
193.1421 Remedial measures
193.1423 Corrosion control records
Appendix A
I. List of Organization and Addresses
II. Documents Incorporated by Reference

Table A.2. General Specifications for Cryogenic Liquid Tank Car Tanks: 49 CFR 179
Subpart F-Specifications for Cryogenic Liquid Tank Car Tanks and Seamless Steel
Tanks (1994 Edition)
Section 179.400 General specifications applicable to cryogenic liquid tank car tanks
179.400-1 General
179.400-2 Approval
179.400-3 Type
179.400-4 Insulation system and performance standard
218 Appendix A

179.400-5 Materials
179.400-6 Bursting and buckling pressure
179.400-7 Tank heads
179.400-8 Thickness of plates
179.400-9 Stiffening rings
179.400-10 Sump or siphon bowl
179.400-11 Welding
179.400-12 Post weld heat treatment
179.400-13 Support system for inner tank
179.400-14 Cleaning of inner tank
179.400-15 Radioscopy
179.400-16 Access to inner tank
179.400-17 Inner tank piping
179.400-18 Test of inner tank
179.400-19 Valves and gages
179.400-20 Pressure relief devices
179.400-21 Test of pressure relief valves
179.400-22 Protective housings
179.400-23 Operating instructions
179.400-24 Stamping
179.400-25 Stenciling
179.400-26 Certificate of construction

Section 179.40 I Individual specification requirements for cryogenic liquid tank car tanks

Table A.3. Outline of OSHA Regulation for Flammable and Combustible Liquids
[Occupational Safety and Health Administration, Labor; 29 CFR Ch. XVII
(7-1-93 Edition)

1926.152 Flammable and combustible liquids


(a) General requirements
(I) Approved containers
(2) Excluded storage areas
(b) Indoor storage of flammable and combustible liquids
(1) Maximum quantity outside storage cabinet
(2) Storage inside storage cabinet
(i) Wooden storage cabinet
(ii) Metal storage cabinet
(iii) Storage cabinet labeling
(3) Maximum quantity inside a storage cabinet
(4) Inside storage room
(i) Fire resistive rating
(ii) Automatic extinguishing system and openings to other rooms
(iii) Storage of materials that react with water
(iv) Maximum storage quantities
(v) Electrical wiring and equipment
(vi) Exhausting system
(vii) Aisle and container stacking
(viii) Storage of quantities exceeding maximum
(5) Quantity near spraying operations and storage of portable containers
(c) Storage outside buildings
(I) Maximum storage in one pile or area
Code of Federal Regulations 219

(2) Access way to pile


(3) Curbs, dikes, drains, and grading of storage area
(4) Outdoor portable tank storage
(i) Separation distances
(ii) Access ways
(5) Storage area cleanliness
(6) Emergency venting and other devices for portable tanks with capacity not exceeding
660 gallons
(7) Emergency venting and other devices for portable tanks with capacity exceeding
660 gallons
(d) Fire control for flammable or combustible liquid storage
(I) Portable fire extinguisher for indoor storage
(2) Portable fire extinguisher for outdoor storage
(3) Sprinklers
(4) Portable fire extinguisher for tank trucks and other transporting vehicles
(e) Dispensing liquids
(I) Separation distance, drainage, and ventilation
(2) Electrical bonding
(3) Transfer system
(4) Protection against collision damage
(5) Dispensing devices and nozzles
(f) Handling liquids at point of final use
(\) Storage containers
(2) Disposal ofleakage or spillage
(3) Separation from ignition sources
(g) Service and refueling areas
(I) Storage containers
(2) Tank trucks
(3) Dispensing hose
(4) Dispensing nozzle
(5) Abandonment of underground tanks
(6) Power shutoff switches
(7) Heating equipment
(i) In lubrication and service area with no dispensing or transferring of flammable
liquids
(ii) In lubrication and service area with dispensing or transferring of flammable liquids
(8) No smoking or open flame areas
(9) Posting of smoking prohibited signs
(10) Motor operation during fueling operation
(\ I) Fire extinguishers
(h) Scope
(i) Tank storage
(\) Design and construction of tanks
(i) Materials
(A) Steel
(B) Other materials allowed for underground storage tanks
(C) Design specifications for other materials
(D) Concrete tanks; lined and unlined
(E) Reserved
(F) Special design considerations for specific gravity less than water or
temperature below 0 F
220 Appendix A

(ii) Fabrication
(A) Reserved
(B) Metal tank fabrication
(iii) Atmospheric tanks
(A) Design and fabrication standards
(I) Underwriters' Laboratories, Inc. No. 142; No. 58; or No. 80
(2) American Petroleum Institute No. 12A or No. 650
(3) American Petroleum Institute No. 12B; No. 12D; or No. 12F
(B) Above-ground use of tanks designed for underground use
(C) Atmospheric tank use oflow-pressure tanks and pressure vessels
(D) Use with flammable or combustible liquid at or above its boiling point
(iv) Low-pressure tanks
(A) Normal operating pressure
(B) Design and fabrication standards
(I) American Petroleum Institute No. 620
(2) ASME Boiler and Pressure Vessel Code
(C) Limits for use of tanks built according to Underwriter's Laboratories standards
(D) Use of pressure vessels for low-pressure tanks
(v) Pressure vessels
(A) Normal operating pressure
(B) Design and fabrication according to ASME Boiler and Pressure Vessel Code
(vi) Provisions for internal corrosion
(2) Installation of outside aboveground tanks
(i) Reserved
(ii) Spacing (shell-to-shell) between aboveground tanks
(A) Separation distance
(B) Separation distance exceptions
(C) Crude petroleum in conjunction with production facilities
(0) Separation distance for unstable flammable or combustible liquids
(E) Tank spacing for compacted three or more rows or for irregular pattern
(F) Spacing for an LPG container and a flammable or combustible liquid
storage tank
(iii) Reserved
(iv) Normal venting for aboveground tanks
(A) Atmospheric storage tank vent
(B) Sizing of normal vents
(C) Venting provisions to prevent pressure or vacuum as a result of filling or
emptying
(D) Venting provisions for multiple fiU or withdrawal connections
(E) Vent location for ignitable vapors
(F) Normally closed vents
(G) Flame arresters
(v) Emergency relief venting for fire exposure for aboveground tanks
(A) Pressure relief of excessive pressure caused by exposure fire
(B) Pressure relieving construction for a vertical tank
(C) Total venting capacity
(0) Total rate of venting determination
(E) Total emergency relief venting capacity determination
(F) Required airflow rate determination
(G) Outlet of vents and vent drains
Code of Federal Regulations 221

(H) Tank venting device identification


(I) Flow test of tank venting devices 12 inches and smaller in nominal pipe size
(vi) Vent piping for aboveground tanks
(A) Construction
(B) Location
(C) Manifolded vent piping
(vii) Drainage, dikes, and walls for aboveground tanks
(A) Drainage and diked areas
(B) Drainage
(C) Diked areas
(1) Volumetric capacity
(2) Volumetric capacity for crude petroleum with boilover characteristics
(3) Dike wall materials
(4) Dike wall height limit
(5) Reserved
(6) Storage within diked area
(viii) Tank openings other than vents for aboveground tanks
(A) Reserved
(B) Reserved
(C) Reserved
(D) Gage opening covering
(E) Fill pipe
(F) Filling and emptying connections
(3) Installation of underground tanks
(i) Location
(ii) Depth and cover
(iii) Corrosion protection
(A) Protective coatings or wrappings
(B) Cathodic protection
(C) Corrosion resistant materials
(iv) Vents
(A) Location and arrangement for Class I liquids
(B) Size
(C) Location and arrangement for Class II and Class III liquids
(D) Construction
(E) Manifolded tank vents
(v) Tank openings other than vents
(A) Connections
(B) Manual gaging opening covering
(C) Fill and discharge lines
(D) Vent piping construction
(E) Manifolded tank vents
(4) Installation of tanks inside of buildings
(i) Location
(ii) Vents
(iii) Vent piping
(iv) Tank openings other than vents
(A) Connections
(B) Connection valves
(C) Automatic-closing heat-actuated valves
222 Appendix A

(D) Covering for manual gaging openings


(E) Fill pipe design
(F) Fill pipe vibration
(G) Location of fill pipe inlet
(H) Overflow prevention
(5) Supports, foundations, and anchorage for all tank locations
(i) General
(ii) Fire resistance
(iii) Spheres
(iv) Load distribution
(v) Foundations
(vi) Flood areas
(A) Storage tank location
(8) Water supply facilities
(C) Additional tank requirements
(D) Horizontal tank location and support
(E) Reserved
(F) Provisions without adequate water supply for resisting external pressures
due to high ground water or flood waters
(G) Provisions with adequate water supply for resisting external pressures due
to high ground water or flood waters
(H) Pipe connections
(I) Independent water supply
(1) Self-contained power and pumping unit
(K) Pumping unit capacity
(L) Pumping unit testing
(M) Structural guides for floating tanks
(N) Lateral movement resistance
(0) Support for swift currents in flood waters
(P) Tank filling for flood protection
(Q) Water pump fuel
(R) Connecting pipe valves
(S) Rigid connections disconnection
(T) Tank valves position
(U) Swing pipe position
(V) Inspections
(1) Compliance
(2) Emergency instructions
(3) Operator training
(vii) Earthquake areas
(6) Sources of ignition
(7) Testing
(i) General
(ii) Strength
(iii) Tightness
(iv) Repairs
(v) Derated operations
(j) Piping, valves, and fittings
(I) General
(i) Design
Code of Federal Regulations 223

(ii)Exceptions
(A) Oil or gas well connections
(B) Engines
(C) Piping per pressure vessel code
(iii) Definitions
(2) Materials for piping, valves, and fittings
(i) Required materials
(ii) Exceptions
(iii) Linings
(iv) Low-melting materials
(3) Pipe joints
(4) Supports
(5) Protection against corrosion
(6) Valves
(7) Testing
(k) Marine service stations
(I) Dispensing
(i) Dispensing area location
(ii) Dispensing units
(iii) Dispensing nozzles
(2) Tanks and pumps
(i) Location of tanks and pumps non-integral to dispensing unit
(ii) Alternative location provisions
(iii) Shore tank location
(iv) Tank outlet location
(3) Piping
(i) Piping between shore tanks and dispensing units
(ii) Shut off valve
(iii) Protection from physical damage
(iv) Grounding
(4) Definition; as used in this section

1926.153 Liquefied petroleum gas (LP-gas)


AppendixB

List of Symbols

Does not include symbols used to denote units, e.g., K for Kelvin.
A Flow area of relief valve
B Parameter defined by Eq. (4.3)
C Expansion factor for flow through relief valve
Ce Capacitance
Cp Specific heat at constant pressure
Cv Specific heat at constant volume
D Diameter of pipe
Di Inside diameter
Do Outside diameter
d Duration of a fire
E Elastic (or Young's) modulus
f Frequency of oscillations
G Mass flux [kg/(sm2)]
Gs Gas mass flow for Baker plot [lbm/(ft2hr)]
gc Unit conversion factor (see Chapter 5)
H Height of a "U" bend in a pipeline (Fig. 4.5)
I Electrical current
K Discharge coefficient for flow through relief valve
k Rate constant for conversion of orthohydrogen to parahydrogen
L Inductance of coil, or length
Ls Liquid mass flow for Baker plot [lbm/(ft2hr)]
LG Length of cryogenic transfer line filled with gas during cool-down
LL Length of cryogenic transfer line filled with liquid during cool-down
Lo Length of a specimen at 0 K
Lp Length of a pipeline containing a "U" bend (Fig. 4.5)
LT Length of a specimen at temperature T; e.g., L300 = length at 300 K
M,MW Molecular weight
m Total mass flow (Ls + GB)
mf Flow rate (kg/s)

225
226 Appendix B

n Number of moles ofa gas


q Heat flux
P Pressure
Pc Critical pressure
P max Pressure in a vessel to operate its relief valve
Pr Reduced pressure
p Amplitude of pressure oscillations
R Gas constant, or electrical resistance
Rf Distance from a flame
T Temperature (absolute)
Tc Critical temperature
Tr Reduced temperature
t Pipe wall thickness, or time
V Volume
Ve Voltage
VG Volume of gas
VL Volume of liquid
W Width of"U" bend (Fig. 4.5)
~ Mass of fuel in a hydrogen fIre
Wmax Maximum flow rate as described in Fig. 4.7
x Concentration of orthohydrogen
Z Compressibility factor
Greek letters
a Aspect ratio (WILp) for "U" bend in pipeline
~ Aspect ratio (HI Lp) for "U" bend in pipeline
y Ratio of specifIc heats (Cpl Cv), or liquid surface tension
Mlv Heat of vaporization
M Change in length
I1T Change in temperature
e Strain
Bt Integrated thermal contraction from ambient temperature to cryogenic
temperature
A. Detonation cell dimension
A Parameter used in Baker's correlation, defIned in caption to Fig. 4.10
qt Parameter used in Baker's correlation, defmed in caption to Fig. 4.10
ilL Liquid viscosity
P Density
PG Gas density
PL Liquid density
cr Stress
List of Symbols 227

Dimensionless numbers (defined in text a/Chapter 5)


Nbo Boiling number
N boi Boiling number for inception of oscillations
N sv Specific volume number
N am Amplitude number
Appendix C

List of Acronyms

AICC Adiabatic, isochoric, complete combustion


AISI American Iron and Steel Institute
ANSI American National Standards Institute
API American Petroleum Institute
ASME American Society of Mechanical Engineers
ASTM American Society for Testing and Materials
bcc Body-centered cubic crystal structure
BLEVE Boiling-liquid--expanding-vapor explosion
CFR Code of Federal Regulations
CGA Compressed Gas Association
CNG Compressed natural gas
CP Critical point
DOD U.S. Department of Defense (also US DOD)
DOT U.S. Department of Transportation (also US DOT)
EP Explosion-proof
fcc Face-centered cubic crystal structure
FM Factory Mutual Engineering and Research
FMEA Failure mode and effects analysis
GH2 Gaseous hydrogen
GN2 Gaseous nitrogen
HAZOP Hazard and operability study
HC Hydrocarbon
hcp Hexagonal close-packed crystal structure
HE Hydrogen embrittlement
IEC International Electrotechnical Commission
ISA Instrument Society of America
ISO International Organization for Standardization
J-T Joule-Thomson expansion process
LFL Lower flammability limit
LH2 Liquid hydrogen

229
230 Appendix C

LNG Liquefied natural gas


LOX Liquid oxygen
LPG Liquefied petroleum gas
MAWP Maximum allowable working pressure
MESG Maximum experimental safe gap
MIE Minimum ignition energy
MRI Magnetic resonance imaging
NASA National Aeronautics and Space Administration
NASP National Aero-Space Plane
NBP Normal boiling point (at I atm pressure)
NFPA National Fire Protection Association
OSHA Occupational Safety and Health Administration
Q-D Quantity-distance relationship for safe storage of a cryogenic liquid
SOP Standard operating procedure
TAO Thermal acoustic oscillations
TP Triple point
UFL Upper flammable limit
UL Underwriters'Laboratory
VI Vaporization index
Index

Accidents Code of federal regulations, 175-\76,213-


Apollo 13 oxygen tank explosion, 208-211 223
causes, 2-3 cryogenic liquid tank cars, 217-218
design considerations, 2, 197-198 flammable and combustible liquids, 218-
helium, 208 223
hydrogen, 3, 93-95, 107-110, 198-203 LNG, 213-217
LNG, I, 19-20,94 Cold embrittlement, 19-24
nitrogen, 203-208 Combustion
oxygen, 208-211 elements required, 79
prevention, 197-198 hazards, 117, 199-203
vent systems, 86-89 hydrogen: see Hydrogen, combustion
Acronyms, 229-230 mixture elimination, 81--86
Apollo 13 oxygen tank explosion, 208-211 pressure rise when confined, 107-110
Asphyxiation, 9, 12-14, 182-183 properties, 10 I-I 08
symptoms, 13-14 rates for metals in oxygen atmosphere,
Autoignition temperature, 102-104 124
rates for nonmetals in oxygen atmosphere,
Baker plot, 48-49 127
Blast overpressure, 95--96 Compressibility factor, 56--57
BLEVE, 93-94 Condensation
Boil-off rate correction, 55 air, 53-54, 59, 65, 73-77, 85, 130, 144
Buoyancy: see Dispersion, buoyancy on cold surfaces, 76, 77
Bum pond, 89 at cryogenic temperatures, 6, 66, 73-77
hazards, 74--76
Carbon dioxide, 5,14--15,73,106,119,150, preventive measures, 77
l71-172 Conductivity
exposure limit, 15 electrical, 81,141,191
Carbon monoxide, 5,15--16,79,119,150,171- thermal, 43, 62, 138, 151, 190
172 Cool-down rate, 43-50
exposure limit, 15--16 Critical constants for cryogens, 57
toxicity, I 5--16 Cryogenic fluid
Charpy impact strength, 21-22 definition, 4
Charpy impact test for embrittlement, 21-22 properties, 4--6, 55, 57, 66, 73, 182
Checklist, 3, 4, 154
Cleaning materials for oxygen service, 128- Deflagration, 95, 101-110, 169, 183, 185, 188,
130 201
Codes: see Regulations maximum pressure rise when confined, 110

231
232 Index

Design review, 2 Hazard and operability study (HAZOP), 197-


Detonation, 101, 106, I la-II 5, 183, 185, 188, 198
201 Hazards
cell size, 112 analysis, 130, 197-198
effect of geometry on propagation, 114 chemical,6
initiation energy, 113 combustion, 79, 199-203
Dike, 20, 192-193,214,221 oxygen, 117
Dimensionless numbers, 67, 227 physical,6
Dispersion physiological, 6, 9-16
buoyancy, 14,82,91, 103, 182 types, 6
convection, 4, 13, 82 from unwanted condensation of higher boil-
diffusion, 13,82,85,87,102-103 ing species, 74
hydrogen, 9a-92 Heat leak correction for boil-off measurements,
leaks and spills, 82,181-184,192-193 55
Hydrogen
accidents, 93-94, 199-203
Electrical charge, 76,141,146,191
combustion, 184-186
static, 8a-81, 141, 184
embrittlement, 24-30
Embrittlement
types of, 24-27
low temperature, 6, 19-24, 74, 76, 83
fire
hydrogen, 24-30, 83
duration, 97-98
avoiding, 29
flame characteristics, 82, 93
characteristics, 25
orthohydrogen to parahydrogen conversion,
effects of, 26-27
141-142, 146, 151
environmental, 26-28
parahydrogen, 137-142, 150
internal, 25-26
properties, 5
material susceptibility, 30
slush: see Slush hydrogen
mechanisms, 2~29
Hypothermia, 9-12
reaction, 24-25
symptoms, 12
types, 24-27
Explosion proof equipment, 80
Ignition
source, 76, 79-81, 87, III, 130, 184-185,
Failure modes and effects analysis, 197 188,191,222
Fire solid-air/liquid-hydrogen mixture, 188
hydrogen, 186, 198 hydrogen releases, 184
duration, 97-98 Instrumentation, 2, 60, 65, 68, 83,162,166,203
water protection system, 93-94, 172, 193, Insulation, 148, 165,214-215
201-202 against cold fluids, 65, 76
prevention, 79 Dewar, 39-41, 57, 62
thermal radiation, 95-97, 185-186 foam and rock wool, 41
Flammability limits, 101-102, 107-108 multilayer, 39, 62, 203
Flow rate limitations to control thermal stress, perlite powder, 39-41, 62
43-50 vacuum, 1,39,41,53-54,62,73,76-77,
Fluorine, 5,15-16 149
exposure limit, 16
toxicity, 16 Leak detection, 3, 82, 148
Freezing of tissue, 6, 9-12 Leakage
prevention, 10 mechanism for dispersion, 82
treatment, II protection against, 82-83
Frostbite: see Freezing of tissue LNG, I, 19-20,69,79,83,88,94-95,99,101-
102,170,176,183-184,187,193,
Guidelines: see Standards 213-217
Index 233

Materials for cryogenic service, 23--24 Quantity-distance relationships for hydrogen


Maximum allowable working pressure, 63-- storage; 98-99, 177, 192-193
64 Quenching of superconducting magnets, 70-
Maximum experimental safe gap, 80 71
Minimum ignition energy, 79,102,104-106
Minimum ignition temperature of nonmetals in
Release of combustible gases, 86-93
oxygen, 126-127
Relief devices: see Pressure, relief devices
Regulations, 4, 159-160, 175-178, 193,213--
Overpressure, 106-107, 186,215
223
flow oscillation, 66-69
Rollover, 69-70
protection, 63--65
quenching of superconducting magnets, 70-
71 Safety
rollover, 69-70 analysis, 2, 197-198
thermal acoustic oscillation, 68--69 codes and regulations, 175-178, 193--194,
thermal expansion, 65-{i6 213--223
Oxygen, 170-173, 176 committee, 2, 3, 197-198
cleaning requirements, 128-130 further investigation needed, 181-192
enrichment upon condensation of air, 65, 73, general requirements, 2-3
75-77,120 guidelines, 159-161, 172
hazards, 117 importance, I
hydrocarbon solubility, 118 standards, 159-174, 193--194
ignitability tests of materials in, 120-123 Slush hydrogen, 86,133--157
metals for service in, 123--125 advantages, 133
nonmetals for service in, 125-127 aging, 146, 150-151, 191-192
properties, 117-118 air contamination, 144, 187-190
purity requirements, 118-120 electrical conductivity, 140-141
Ozone heat of transition, 139-140
exposure limit, 15 melting pressure as a function of tempera-
explosive decomposition, 131 ture, 138-139
properties, 5, 131 orthohydrogen-parahydrogen equilibrium,
toxicity, 15, 131 141-142
pressure control, 144-145, 147, 151-152,
Perlite compaction, 39-41 190-191
Pilatre de Rozier, 3 production techniques, 144, 149-150
Protective equipment, 10-11 properties, 133--143, 147
Pressure safety hazards, 136, 144-146, 186-192
buildup, 53--71, 207 solubility of helium, 142-143, 152
caused by quenching of superconducting system design, 147-150
magnets, 70-71 transfer, 154
caused by thermal expansion, 65-{i6 vapor pressure, 136-137
in closed systems, 6, 53, 59-63, 203--208 volume expansion, 146, 153
maximum, 53 Spills onto water, 183--184
rise rate, 55-{i2 Standard operating procedure, 3--4, 153--154
in volumes that need overpressure protec- Standards, 159-174, 177-178, 185, 192-
tion, 53--54 193
oscillations, 51, 66-69, 145, 153 Static charge: see Electrical charge, static
relief devices, 53, 63--66, 77, 94,147,162, Stratification, 46-47, 57--62, 138, 144-145,
167,171,199,215,218 151-152,155,190,215
relief panels, 109, 114 Stress, 20, 50
Protection against valve leakage, 82---83 allowable, 38
Purging, 74, 77,80,84---86,169,171 dimensional change, 33--43
234 Index

Stress (cont.) Toxicity, 9,15-16,125,131


thermal, 6, 33 Training, 3, 4, 99, 147, 197-198,207-208,
flow rate limitations, 43-50 212,216-217
thermal gradient, 6, 43-49
yield, tensile, ultimate, 22-23, 26 "U" bend, 42-43
Stress--strain relationship, 20 Ullage space, 66, 68,146,152-153,155
Symbols, 225-227
Valve leakage protection, 82-84
Thermal acoustic oscillations, 68--69, 145, Vaporization index, 5, 6, 62
153 Vapor pressure at low temperature, 73
Thermal contraction: see Thermal expansion Ventilation, 12-13
Thermal expansion, 6, 33-43 Vent, 13,53,58-59,86-87,147,151,153,207-
coefficients for cryogens, 65--66 208,216,220
metals, 33-36 orientation, II
overpressure, 65 system, 63--66, 86,147,168,193,199
plastics, 36 velocity, 80, 87-88, 200
transfer lines and piping, 41-43 Venting combustible gases, 80, 86-93, 169,
Thermal radiation, 88, 95-99, 213 182-183,190,200-203
effects, 96-97, 185-186 dispersion of vented gas, 82, 90-92
Thermal stresses extinguishing vent fires, 92"'-93
caused by thermal gradients, 43-50 flared venting, 87-89
reliefby providing flexibility, 42-43 unflared venting, 86-87
in transfer lines, 41-43 venting versus flaring, 90-93, 183, 185