Cryogenic techniques

Cryogenics is the study of the production of very low temperature(below 123 K) and the
behaviour of materials at those temperature.

Cryogenic substances are liquefied gases that are kept in their liquid state at very low
temperatures e.g. nitrogen, oxygen, carbon dioxide, helium and argon.

Classification of cryogenic fluids

Regardless of the individual characteristics of cryogenic fluids, almost all of them can be
grouped into one of three main groups for classification:

 Inert gases: These gases do not exhibit any significant chemical reaction. They don’t
burn or allow combustion. They include nitrogen, helium, neon, argon and krypton.

 Flammable gases: The gas produced by these cryogenic liquids can burn in the air. The
most common examples are hydrogen, methane and liquefied natural gas.

 Oxygen: Many of the materials considered ‘non-combustible’ can burn in the presence
of liquid oxygen. Organic materials can react explosively with liquid oxygen. The hazards
and precautions associated with handling liquid oxygen must therefore be considered
separately.

Cryogenics is used in a variety of applications. It can be used to produce cryogenic fields for
rockets, in MRI machines that use liquid helium and require cryogenic cooling, storing large
quantities of food, special effects fog, recycling, freezing blood and tissue samples, and even
cooling superconductors.

How are cryogenic temperatures achieved?

To achieve freezing temperatures, sophisticated techniques are required. In most cases, four
different methods are used to generate cryogenic temperatures:

1. Thermal conductivity

Thermal conduction is perhaps the most familiar method. By bringing two products or materials
into contact, heat transfers from the hottest product to the coldest product. The same principle
applies for cryogenic temperatures. The extreme cold is transmitted by bringing a gas, a liquid,
or a solid into contact with a cryogenic liquid. The gas, liquid, or solid, as a result, also reaches
the desired cryogenic temperature.

2. Evaporative Cooling

Atoms or molecules have less energy in liquid form than they have in a gaseous form. During
the evaporation of a liquid product, atoms or molecules on the surface receive enough energy
from the surrounding liquid to convert to its gaseous state. In contrast, the remaining liquid
retains less energy, making it colder. Thus, by inducing an evaporation process, the cooling of a
liquid can be achieved.

3. Cooling by rapid expansion

A third method is the use of the Joule-Thompson effect. This involves cooling gases by an
abrupt expansion of volume or an equally fast pressure drop. This method is extensively used in
liquefying hydrogen and helium.

4. Adiabatic demagnetization

The fourth and final method is mainly used in the cooling of liquid helium and involves
paramagnetic salts to absorb heat. Paramagnetic salt can be thought of as a massive number of
small magnets that, when placed on a strong magnetic field and processed with an
electromagnet, generate or use energy. By absorbing the energy with these materials from a
gas, the gas becomes colder and colder.

HAZARDS

Cryogenic liquids are liquids that exist between -66ºC and -266ºC. The most common cryogens
used in the laboratory are liquid nitrogen, liquid helium and solid carbon dioxide (dry ice),
although there are others including liquid oxygen and liquid argon.

Carbon Dioxide
Property Oxygen (02) Nitrogen (N2) Argon (Ar) Helium (He)
(C02)

Molecular
32 28 40 4 44
weight

Colour of gas None None None None None

Colour of liquid Light blue None None None None

Boiling point
(ºC) at -78.5
-183 -196 -186 -269
atmospheric (Sublimes)
pressure

Ratio of
volume gas to
842 682 822 738 845 (Solid)
liquid at 15ºC
101.3kPa

Explosive/fire
Yes No No No No
danger

Toxic No No No No Mildly

Due to the great expansion ratio of cryogenic gases, a spillage can result in significant oxygen
depletion within the room, which may be life threatening.

Hazards

1.1 Cold burns, frostbite and hypothermia

 Contact of the skin with cryogenic liquids (or even cold gas) can cause severe cryogenic
burns; prolonged exposure of the skin or contact with cold surfaces can cause frostbite.
The skin appears waxy yellow. There is no initial pain, but as the frozen tissue thaws
intense pain might be experienced. the tissue damage that results is similar to that
caused by frost bite or thermal burns. While the cold itself can reduce the feeling of
pain, the subsequent thawing of tissue can cause intense pain.

 Unprotected skin can stick to metal that is cooled by cryogenic substance and can then
tear when pulled away. Even non-metallic materials are dangerous to touch at low
temperatures.

 Prolonged breathing of extremely cold air may damage the lungs, while short exposure
may provoke an asthma attack in susceptible people.

 Hypothermia is risk due to the low temperatures arising from the proximity of cryogenic
liquids. Risk is dependent upon the length of exposure, the atmospheric temperature
and the individual; those exposed for prolonged periods should be warmly clothed
  The low viscosity of cryogenic liquids means that they will penetrate woven or other
porous clothing materials much faster than, for example, water.

 Controls
Avoid direct contact with a cryogen or objects frozen using a cryogen. DO NOT
grasp cold metal surfaces with unprotected skin.
Use cryogenic gloves with tongs and dippers to withdraw or immerse objects further
information.
When working with cryogens remove watches, wrist-bands or bracelets which
may trap liquid cryogens close to the skin.

1.2 Oxygen deficiency and asphyxiation

In poorly ventilated areas these cryogenic gases can easily decrease the percentage of
oxygen in air and cause asphyxiation.

Whilst not toxic themselves (excepting CO2 which is mildly toxic), the cryogenic gases are
capable of causing asphyxiation by displacing the air necessary to support life.

A reduction in atmospheric oxygen results in loss of mental alertness and distortion of judgement
and performance. This occurs in a relatively short time period and without the person being
aware it is happening.

An oxygen shift as low as 3% below 20.9% (normal air concentration) is potentially

dangerous and atmospheres containing less than 10% oxygen can be fatal.

Upon evaporation, the volume of cryogenic liquid expands approximately 700 - 900 times its
volume in the gaseous form. If this occurs in a room that is inadequately ventilated, atmospheric
oxygen will be displaced. This will result in the oxygen content of the air being reduced to such
an extent that it will not sustain life.

The onset of oxygen deficiency problems is often not apparent to the individual involved as there
are few warning signs. In going to assist unconscious colleagues, rescuers themselves are often
overcome by the lack of oxygen, resulting in further fatalities.

N.B. If you find someone unconscious and suspecting asphyxiation, the alarm should be
raised and you should activate the Emergency Action Plan for a Major Release of Toxic Gas,
Low Temperature Liquefied Gas or Major Spillage of Hazardous Substance

Controls
Before handling cryogens or entering an area where they are stored, always
check there is adequate ventilation
If such ventilated areas are not available, then oxygen monitoring equipment
should be fitted in line with the Air and Health Monitoring Guidelines and
Local WHS Monitoring Equipment Form.Avoid spills

1.3 Increased flammability from oxygen enrichment

Although itself not flammable oxygen, when present in higher concentrations, can significantly
increase the chance of fire or an explosion.

The boiling point of oxygen is above those of nitrogen and helium. In closed systems (such as
cold traps cooled with liquid nitrogen) these liquids can cause oxygen to condense on their
surface (resulting in a bluish liquid on the surface). This can lead to the ignition of normally non-
combustible materials and the flammability limits of flammable gases and vapours are widened.
Oil and grease may spontaneously ignite and as such should not be used where oxygeenrichment
may occur.

Controls

DO NOT permit liquid oxygen or oxygen rich atmosphere to come into contact with organic
materials or flammable substances of any kind.
It is recommended that whenever possible some coolant should be used in preference to cryogens
(e.g. baths containing isopropanol or glycols).
When liquid cryogens or Dry Ice are used to cool traps attached to vacuum pumps, these traps
must be emptied immediately after use.
DO NOT leave cold traps immersed in the cryogen.
DO NOT release the vacuum of any evacuated vessel while liquid nitrogen is present.

1.4 Pressure build up / Explosions

Cryogenic liquids vaporise with a volume change ratio of 700-900 and can thus cause violent
changes in pressure, particularly if this occurs in a confined space. This in turn can result in an
explosion. Vent systems must be in place to allow gas to escape from confined spaces.
Pressurisation can occur due to the following:

 Ice forming on the venting tube, plugging it and preventing gas release;
 Damaged equipment resulting in cryogenic fluids leaking into small areas. Upon
vaporisation the cryogenic liquid vaporises and causes pressure build up;
 Loss of vacuum inside a cryostat or dewar;
 If a liquid helium-cooled super-conducting magnet "quenches" (changes spontaneously
from a super-conducting state to a normal state);
 Liquid nitrogen having permeated through sealed cryo-tubes containing samples which
then return to room temperature;
 Direct contact of the cryogenic liquid with water in a tube results in rapid vaporisation of
the cryogenic liquid and can cause the tube to explode.
 Controls
It is critical to contain these liquids in insulated Dewars with pressure relief valves
DO NOT put cryogens in closed vessels that cannot withstand the pressure (e.g. capped
Thermos flasks).
Ensure safety valves are operational on withdrawal devices

1.5 Damage to Equipment /Thermal stress to materials

The very cold temperatures of cryogenic liquids can damage equipment and materials, which can
result in danger.

 Spilled liquid nitrogen can crack tiles and damage flooring such as vinyl;
 Rubber tubing may become brittle and crack during use;
 Condensation of water around electrical cables may result in an electrical shock hazard.
Controls
Cryogenic storage and transport vessels should be filled slowly to minimise thermal
shock
Pour liquid cryogens only into suitable storage and transport vessels (i.e. not glassware)
Always place materials slowly into cryogens

1.6 Flammable Gas - Hydrogen

Hydrogen is extremely flammable and should be treated with extreme caution. Areas of use
should be restricted, clearly marked and well ventilated. No naked flames, electrical ignition
sources or potentially combustible materials should be allowed within the restricted area as any
of these could result in an explosion if gas has escaped.

Liquid hydrogen can condense oxygen from air resulting in an explosion hazard. For this reason
closed hydrogen systems should be used to prevent back-flow of air.

1.7 Eye injury

Description Brief exposures to cryogenic substances that would not affect the skin on the face or
hands can damage delicate tissues such as the eyes. Liquid cryogens can splash (possibly in eyes)
while being poured. Additionally, rapid splashing and boiling of cryogens occurs when
dispensing into a warm container (e.g. at room temperature) or when inserting warm objects into
the cryogenic liquid. Flying chunks of frozen debris or cryogen could also cause eye injury.
Controls
To protect the eyes when handling cryogens, always wear safety goggles. Where possible or
when transferring large volumes (>4 L), use a face shield
Always perform operations slowly to minimise boiling and splashing

Storage
Cryogenic storage vessels Liquid cryogenic storage vessels (also known as Dewars) are
specialised vacuum flasks that may take several different forms including open buckets, flasks
with loose-fitting stoppers and self-pressurising tanks. They are designed to reduce the risk
associated with storing liquid cryogens. All Dewars have walls constructed from two or more
layers, with a high vacuum maintained between the layers. This provides very good thermal
insulation between the interior and exterior of the Dewar, which reduces the rate at which the
contents boil off. Precautions are taken in the design of Dewars to safely manage the gas which
is released as the liquid slowly boils. The simplest Dewars (non-pressurised) allow the gas to
escape either through an open top or past a loose-fitting stopper to prevent the risk of
explosion. More sophisticated Dewars (pressurised) trap the gas above the liquid and hold it at
high pressure. This increases the boiling point of the liquid and allows it to be stored for
extended periods. Excessive vapour pressure is released automatically through safety valves.
The method of decanting liquid from a Dewar depends upon its design - refer Section 0. Simple
Dewars may be tilted, to pour liquid from the neck. Selfpressurising designs use the gas
pressure in the top of the Dewar to force the liquid upward through a pipe (spear) leading to
the neck (known as dispensing). There are several types of storage vessels for cryogenic liquids
commonly used on campus and in the field

Transportation
Transporting cryogens in an enclosed space such as a lift or vehicle cabin is extremely
hazardous. Under no circumstance should a person accompany cryogens in a confined space.
Secure storage vessels (such as Dewars) firmly to limit movement when transporting to the field
or refilling. When using depressurized vessels, tape the cap down loosely to prevent it from
falling off whilst still allowing ventilation.