Disclaimer: These guidelines were developed under contract using generally accepted secondary sources. The protocol used by the contractor for surveying these data sources was developed by the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA), and the Department of Energy (DOE). The information contained in these guidelines is intended for reference purposes only. None of the agencies have conducted a comprehensive check of the information and data contained in these sources. It provides a summary of information about chemicals that workers may be exposed to in their workplaces. The secondary sources used for supplements 111 and 1V were published before 1992 and 1993, respectively, and for the remainder of the guidelines the secondary sources used were published before September 1996. This information may be superseded by new developments in the field of industrial hygiene. Therefore readers are advised to determine whether new information is available.
OCCUPATIONAL SAFETY AND HEALTH GUIDELINE FOR DIBORANE
INTRODUCTION
This guideline summarizes pertinent information about diborane for workers
and employers as well as for physicians, industrial hygienists, and other
occupational safety and health professionals who may need such information to
conduct effective occupational safety and health programs. Recommendations
may be superseded by new developments in these fields; readers are therefore
advised to regard these recommendations as general guidelines and to
determine whether new information is available.
SUBSTANCE IDENTIFICATION
* Formula
B(2)H(6)
* Structure
(For Structure, see paper copy)
* Synonyms
Boroethane, boron hydride, diboron hexahydride
* Identifiers
1. CAS No.: 19287-45-7
2. RTECS No.: HQ9275000
3. DOT UN: 1911 18
4. DOT label: Flammable Gas, Poison Gas
* Appearance and odor
Diborane is a colorless gas with a repulsive, sweet odor. It is
sometimes shipped as a liquid pressurized refrigerant. An air odor threshold
of 2.5 parts per million (ppm) parts of air has been reported.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 27.7
2. Boiling point (at 760 mm Hg): -92.5 degrees C (-134.5 degrees F)
3. Specific gravity (water = 1): 0.21 at 15 degrees C (59 degrees F)
4. Vapor density (air = 1): 0.96
5. Melting point: -165 degrees C (-265 degrees F)
6. Vapor pressure at 20 degrees C (68 degrees F): Greater than 760 mm Hg
7. Solubility: Ignites spontaneously in moist air or in contact with
water and decomposes rapidly to form hydrogen gas; soluble in concentrated
sulfuric acid, ammonium hydroxide, and carbon disulfide.
8. Evaporation rate: Not applicable.
* Reactivity
1. Conditions contributing to instability: Temperatures above -18 degrees
C (-O.4 degrees F). Ignites spontaneously in moist air at room temperature.
2. Incompatibilities: Contact between diborane and air or halogenated
compounds will cause fires and explosions. Reacts with water to form
hydrogen and boric acid. Contact with aluminum, lithium, and other active
metals forms hydrides that may ignite spontaneously. Diborane reacts with
many oxidized surfaces as a strong reducing agent.
3. Hazardous decomposition products: Toxic gases and vapors such as
hydrogen gas and boron oxide smoke may be released in a fire involving
diborane.
4. Special precautions: Diborane will attack some forms of plastics,
rubber, and coatings.
* Flammability
The National Fire Protection Association has assigned a flammability
rating of 4 (extreme fire hazard) to diborane.
1. Flash point: Not applicable (gas).
2. Autoignition temperature: 38 to 52 degrees C (100 to 125 degrees F)
3. Flammable limits in air (percent by volume): Lower, 0.8; upper, 88.
4. Extinguishant: Let small fires burn unless leak can be stopped
immediately. Use water spray, fog, or regular foam to fight large fires
involving diborane. Caution should be taken when using water because violent
reactions may result.
Fires involving diborane should be fought upwind from the maximum
distance possible. Keep unnecessary people away; isolate the hazard area and
deny entry. Isolate the area for 1/2 mile in all directions if a tank, rail
car, or tank truck is involved in the fire. For a massive fire in a cargo
area, use unmanned hose holders or monitor nozzles; if this is impossible,
withdraw from the area and let the fire burn. Emergency personnel should
stay out of low areas and ventilate closed spaces before entering. Vapors
may travel to a source of ignition and flash back. Vapors are an explosion
and poison hazard indoors, outdoors, or in sewers. Containers of diborane
may explode in the heat of the fire and should be moved from the fire area if
it is possible to do so safely. If this is not possible, cool fire exposed
containers from the sides with water until well after the fire is out. Stay
away from the ends of containers. Personnel should withdraw immediately if a
rising sound from a venting safety device is heard or if there is
discoloration of a container due to fire. Firefighters should wear a full set
of protective clothing and self-contained breathing apparatus when fighting
fires involving diborane.
EXPOSURE LIMITS
* OSHA PEL
The current Occupational Safety and Health Administration (OSHA)
permissible exposure limit (PEL) for diborane is 0.1 ppm (0.1 milligrams per
cubic meter (mg/m(3))) as an 8-hour time-weighted average (TWA) concentration
[29 CFR 1910.1000, Table Z-1].
* NIOSH REL
The National Institute for Occupational Safety and Health (NIOSH)
has established a recommended exposure limit (REL) for diborane of 0.1 ppm
(0.1 mg/m(3)) as a TWA for up to a 10-hour workday and a 40-hour workweek
[NIOSH 1992].
* ACGIH TLV
The American Conference of Governmental Industrial Hygienists
(ACGIH) has assigned diborane a threshold limit value (TLV) of 0.1 ppm (0.11
mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour workweek [ACGIH
1994, p. 18].
* Rationale for Limits
The NIOSH limit is based on the risk of pulmonary irritation; liver
and kidney damage in animals [NIOSH 1992].
The ACGIH limit is based on the risk of acute poisoning of the lungs
and cumulative effects of the nervous system [ACGIH 1991, p. 393].
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to diborane can occur through inhalation and eye or skin
contact [Sittig 1991].
* Summary of toxicology
1. Effects on Animals: Diborane is a respiratory irritant; it causes
pulmonary edema and central nervous system intoxication in experimental
animals [ACGIH 1991]. The inhalation 4-hour LC(50) in rats is about 50 ppm
(40 mg/m(3)); the corresponding LC(50) for mice is 30 ppm. Seventeen of 18
rats exposed to 7 ppm diborane for six hours/day for 6 months died at
intervals ranging from the 7th to the 113th exposure; dogs exposed on the
same regimen began to die after the 10th exposure. When exposures were
reduced to between 1 and 2 ppm, some dogs survived for 6 months. Mortality
in both rats and dogs was attributed to respiratory complications resulting
from repeated exposure [ACGIH 1991]. In other animal studies, acute exposure
caused pulmonary edema, hemorrhage, and temporary damage to the liver and
kidneys [Hathaway et al. 1991].
2. Effects on Humans: Diborane is primarily an irritant of the
respiratory tract. Over exposure to diborane causes symptoms and signs
similar to those seen in metal fume fever. Observations over a 5-year period
involving 26 cases of acute diborane poisoning and 33 subacute episodes
showed that the predominant effects of diborane poisoning are
bronchopulmonary. Two cases of pneumonitis occurred, and one case of chronic
respiratory distress [Clayton and Clayton 1982]. In chronic exposure, an
increase in non-protein blood nitrogen and cephalin flocculation tests has
been reported, indicating possible liver damage. Diborane may also damage
the kidneys and nervous system [Genium 1987; Parmeggiani 1983; NJDH 1986].
In high concentrations, diborane may be irritating to the eye. Inhalation of
this chemical has also been reported to cause double vision and difficulty in
focusing, which disappeared shortly after exposure ceased [Grant 1986].
Contact with diborane in the liquid form may cause frostbite and cold burns
of the skin or eye [DOT 1993, Guide 18].
* Signs and symptoms of exposure
1. Acute exposure: In acute poisoning, the symptoms are similar to those
of metal fume fever: shortness of breath; coughing; tightness, heaviness,
and burning in the chest; nausea; shivering; fever; and chest pain over the
heart. Other symptoms of acute inhalation are drowsiness, dizziness, double
vision, and difficulty in focusing. Signs appeared shortly after exposure or
after a latent period of up to 24 hours [Sittig 1991]. Skin contact with the
liquid will cause freeze burns. Eye burning and tearing may result from
exposure to high concentrations of the gas [Genium 1987].
2. Chronic exposure: Chronic exposure causes lung irritation, headaches,
dizziness, muscle fatigue, and weakness. There may also be occasional
transient tremors [Parmeggiani 1983].
EMERGENCY MEDICAL PROCEDURES
* Emergency medical procedures: [NIOSH to supply]
5. Rescue: Remove an incapacitated worker from further exposure and
implement appropriate emergency procedures (e.g., those listed on the
Material Safety Data Sheet required by OSHA's Hazard Communication Standard
[29 CFR 1910.1200]). All workers should be familiar with emergency
procedures, the location and proper use of emergency equipment, and methods
of protecting themselves during rescue operations.
EXPOSURE SOURCES AND CONTROL METHODS
The following operations may involve diborane and lead to worker exposures
to this substance:
* The manufacture and transportation of diborane * Use as a reducing
agent in the synthesis of organic chemical intermediates; use in the
conversion of olefins to trialkyl and triaryl boranes and primary alcohols,
and as a polymerization catalyst for ethylene, vinyl, styrene, and butadiene;
use as a chemical intermediate in production of other boron hydrides * Use
in electronics industry to improve crystal growth or to impart electrical
properties in pure crystals; use as a doping agent for p-type semi-conductors
* Use as a rubber vulcanizer; use in the production of hard boron coatings
on metals and ceramics * Use as a component or additive for high-energy
fuels, and as a flame-speed accelerator, and fuel for air-breathing engines
and rockets
Methods that are effective in controlling worker exposures to diborane,
depending on the feasibility of implementation, are as follows:
* Process enclosure * Local exhaust ventilation * General dilution
ventilation * Personal protective equipment
Workers responding to a release or potential release of a hazardous
substance must be protected as required by paragraph (q) of OSHA's Hazardous
Waste Operations and Emergency Response Standard [29 CFR 1910.120].
Good sources of information about control methods are as follows:
1. ACGIH [1992]. Industrial ventilation--a manual of recommended
practice. 21st ed. Cincinnati, OH: American Conference of Governmental
Industrial Hygienists.
2. Burton DJ [1986]. Industrial ventilation--a self study companion.
Cincinnati, OH: American Conference of Governmental Industrial Hygienists.
3. Alden JL, Kane JM [1982]. Design of industrial ventilation systems.
New York, NY: Industrial Press, Inc.
4. Wadden RA, Scheff PA [1987]. Engineering design for control of
workplace hazards. New York, NY: McGraw-Hill.
5. Plog BA [1988]. Fundamentals of industrial hygiene. Chicago, IL:
National Safety Council.
MEDICAL SURVEILLANCE
OSHA is currently developing requirements for medical surveillance. When
these requirements are promulgated, readers should refer to them for
additional information and to determine whether employers whose employees are
exposed to diborane are required to implement medical surveillance
procedures.
* Medical Screening
Workers who may be exposed to chemical hazards should be monitored
in a systematic program of medical surveillance that is intended to prevent
occupational injury and disease. The program should include education of
employers and workers about work-related hazards, early detection of adverse
health effects, and referral of workers for diagnosis and treatment. The
occurrence of disease or other work-related adverse health effects should
prompt immediate evaluation of primary preventive measures (e.g., industrial
hygiene monitoring, engineering controls, and personal protective equipment).
A medical surveillance program is intended to supplement, not replace, such
measures. To detect and control work-related health effects, medical
evaluations should be performed (1) before job placement, (2) periodically
during the term of employment, and (3) at the time of job transfer or
termination.
* Preplacement medical evaluation
Before a worker is placed in a job with a potential for exposure to
diborane, a licensed health care professional should evaluate and document
the worker's baseline health status with thorough medical, environmental, and
occupational histories, a physical examination, and physiologic and
laboratory tests appropriate for the anticipated occupational risks. These
should concentrate on the function and integrity of the respiratory and
central nervous systems. Medical surveillance for respiratory disease should
be conducted using the principles and methods recommended by the American
Thoracic Society.
A preplacement medical evaluation is recommended to assess medical
conditions that may be aggravated or may result in increased risk when a
worker is exposed to diborane at or below the prescribed exposure limit. The
health care professional should consider the probable frequency, intensity,
and duration of exposure as well as the nature and degree of any applicable
medical condition. Such conditions (which should not be regarded as absolute
contraindications to job placement) include a history and other findings
consistent with diseases of the respiratory or central nervous
systems.
* Periodic medical evaluations
Occupational health interviews and physical examinations should be
performed at regular intervals during the employment period, as mandated by
any applicable Federal, State, or local standard. Where no standard exists
and the hazard is minimal, evaluations should be conducted every 3 to 5 years
or as frequently as recommended by an experienced occupational health
physician. Additional examinations may be necessary if a worker develops
symptoms attributable to diborane exposure. The interviews, examinations,
and medical screening tests should focus on identifying the adverse effects
of diborane on the respiratory or central nervous systems. Current health
status should be compared with the baseline health status of the individual
worker or with expected values for a suitable reference population.
* Termination medical evaluations
The medical, environmental, and occupational history interviews, the
physical examination, and selected physiologic or laboratory tests that were
conducted at the time of placement should be repeated at the time of job
transfer or termination to determine the worker's medical status at the end
of his or her employment. Any changes in the worker's health status should
be compared with those expected for a suitable reference
population.
* Biological monitoring
Biological monitoring involves sampling and analyzing body tissues
or fluids to provide an index of exposure to a toxic substance or metabolite.
No biological monitoring test acceptable for routine use has yet been
developed for diborane.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne diborane is made using a
fluoropore filter in series with a charcoal tube (type 580-20,
Barnebey-Cheney) impregnated charcoal (100/50 mg sections). Samples are
collected at a maximum flow rate of 1.0 liter/minute until a minimum
collection volume of 120 liter or maximum collection volume of 260 liters is
reached. Analysis is conducted by inductively coupled plasma using atomic
emission spectroscopy, ICP/DCP-AES. This method (OSHA modified NIOSH method
# 6006) is described in the OSHA Computerized Information System [OSHA 1994]
and is not yet validated. NIOSH Method No. 6006 can also be used to
determine a worker's exposure to airborne diborane [NIOSH 1994b].
PERSONAL HYGIENE PROCEDURES
Workers should not eat, drink, use tobacco products, apply cosmetics, or
take medication in areas where diborane is handled, processed, or stored.
STORAGE
Diborane should be stored in a cool, dry, well-ventilated area in tightly
sealed containers that are labeled in accordance with OSHA's Hazard
Communication Standard [29 CFR 1910.1200]. Containers of diborane should be
protected from physical damage and ignition sources, and should be stored
separately from air, halogenated compounds, water, aluminum, lithium, other
active metals, and any oxidized surfaces. Storage should be below 20 degrees
C (68 degrees F) in a detached, well-ventilated, refrigerated area.
Containers must be clean, dry, and free of oxygen, and should be checked
periodically for decomposition. Dry nitrogen purges should be used for
transfer operations.
SPILLS AND LEAKS
In the event of a spill or leak involving diborane, persons not wearing
protective equipment and fully-encapsulating, vapor-protective clothing
should be restricted from contaminated areas until cleanup has been
completed. The following steps should be undertaken following a spill or
leak:
1. Notify safety personnel.
2. Remove all sources of heat and ignition.
3. Ventilate potentially explosive atmospheres.
4. Stop the leak if it is possible to do so without risk.
5. Use non-sparking tools.
6. Use water spray to reduce vapors; prevent spray water from entering
sewers.
7. If the source of the leak is a cylinder and cannot be stopped in place,
remove the leaking cylinder to open air and repair the leak, or allow the
cylinder to empty. If possible, dilute the leak with an inert gas and
exhaust through a fume hood. Extreme caution should be taken since diborane
will ignite spontaneously.
SPECIAL REQUIREMENTS
U.S. Environmental Protection Agency (EPA) requirements for emergency
planning, reportable quantities of hazardous releases, community
right-to-know, and hazardous waste management may change over time. Users
are therefore advised to determine periodically whether new information is
available.
* Emergency planning requirements
Employers owning or operating a facility at which there are 100
pounds or more of diborane must comply with EPA's emergency planning
requirements [40 CFR Part 355.30].
* Reportable quantity requirements for hazardous releases
A hazardous substance release is defined by EPA as any spilling,
leaking, pumping, pouring, emitting, emptying, discharging, injecting,
escaping, leaching, dumping, or disposing into the environment (including the
abandonment or discarding of contaminated containers) of hazardous
substances. In the event of a release that is above the reportable quantity
for that chemical, employers are required to notify the proper Federal,
State, and local authorities [40 CFR 355.40].
The reportable quantity of diborane is 1 pound. If an amount equal
to or greater than this quantity is released within a 24-hour period in a
manner that will expose persons outside the facility, employers are required
to do the following:
- Notify the National Response Center immediately at (800)
424-8802 or at (202) 426-2675 in Washington, D.C. [40 CFR 302.6].
- Notify the emergency response commission of the State likely to
be affected by the release [40 CFR 355.40].
- Notify the community emergency coordinator to the local
emergency planning committee (or relevant local emergency response personnel)
of any area likely to be affected by the release [40 CFR 355.40].
* Community right-to-know requirements
Employers are not required by EPA in 40 CFR Part 372.30 to submit a
Toxic Chemical Release Inventory form (Form R) to EPA reporting the amount of
diborane emitted or released from their facility annually.
* Hazardous waste management requirements
EPA considers a waste to be hazardous if it exhibits any of the
following characteristics: ignitability, corrosivity, reactivity, or
toxicity as defined in 40 CFR 261.21-261.24. Under the Resource Conservation
and Recovery Act (RCRA) [40 USC 6901 et seq.], EPA has specifically listed
many chemical wastes as hazardous. Although diborane is not specifically
listed as a hazardous waste under RCRA, EPA requires employers to treat waste
as hazardous if it exhibits any of the characteristics discussed
above.
Providing detailed information about the removal and disposal of
specific chemicals is beyond the scope of this guideline. The U.S.
Department of Transportation, EPA, and State and local regulations should be
followed to ensure that removal, transport, and disposal of this substance
are conducted in accordance with existing regulations. To be certain that
chemical waste disposal meets EPA regulatory requirements, employers should
address any questions to the RCRA hotline at (703) 412-9810 (in the
Washington, D.C. area) or toll-free at (800) 424-9346 (outside Washington,
D.C.). In addition, relevant State and local authorities should be contacted
for information on any requirements they may have for the waste removal and
disposal of this substance.
RESPIRATORY PROTECTION
* Conditions for respirator use
Good industrial hygiene practice requires that engineering controls
be used where feasible to reduce workplace concentrations of hazardous
materials to the prescribed exposure limit. However, some situations may
require the use of respirators to control exposure. Respirators must be worn
if the ambient concentration of diborane exceeds prescribed exposure limits.
Respirators may be used (1) before engineering controls have been installed,
(2) during work operations such as maintenance or repair activities that
involve unknown exposures, (3) during operations that require entry into
tanks or closed vessels, and (4) during emergencies. Workers should only use
respirators that have been approved by NIOSH and the Mine Safety and Health
Administration (MSHA).
* Respiratory protection program
Employers should institute a complete respiratory protection program
that, at a minimum, complies with the requirements of OSHA's Respiratory
Protection Standard [29 CFR 1910.134]. Such a program must include
respirator selection, an evaluation of the worker's ability to perform the
work while wearing a respirator, the regular training of personnel,
respirator fit testing, periodic workplace monitoring, and regular respirator
maintenance, inspection, and cleaning. The implementation of an adequate
respiratory protection program (including selection of the correct
respirator) requires that a knowledgeable person be in charge of the program
and that the program be evaluated regularly. For additional information on
the selection and use of respirators and on the medical screening of
respirator users, consult the latest edition of the NIOSH Respirator Decision
Logic [NIOSH 1987b] and the NIOSH Guide to Industrial Respiratory Protection
[NIOSH 1987a].
PERSONAL PROTECTIVE EQUIPMENT
Workers should use appropriate personal protective clothing and equipment
that must be carefully selected, used, and maintained to be effective in
preventing skin contact with diborane. The selection of the appropriate
personal protective equipment (PPE) (e.g., gloves, sleeves, encapsulating
suits) should be based on the extent of the worker's potential exposure to
diborane. The resistance of one PPE material to permeation by diborane is
shown below:
Material |
Breakthrough time (hr) |
|
butyl rubber |
<1(*) |
(*) Not recommended, degradation may occur
To evaluate the use of this or other PPE materials with diborane, users
should consult the best available performance data and manufacturers'
recommendations. Significant differences have been demonstrated in the
chemical resistance of generically similar PPE materials (e.g., butyl)
produced by different manufacturers. In addition, the chemical resistance of
a mixture may be significantly different from that of any of its neat
components.
Any chemical-resistant clothing that is used should be periodically
evaluated to determine its effectiveness in preventing dermal contact. Safety
showers and eye wash stations should be located close to operations that
involve diborane.
Splash-proof chemical safety goggles or face shields (20 to 30 cm long,
minimum) should be worn during any operation in which a solvent, caustic, or
other toxic substance may be splashed into the eyes.
In addition to the possible need for wearing protective outer apparel (e.g.,
aprons, encapsulating suits), workers should wear work uniforms, coveralls,
or similar full-body coverings that are laundered each day. Employers should
provide lockers or other closed areas to store work and street clothing
separately. Employers should collect work clothing at the end of each work
shift and provide for its laundering. Laundry personnel should be informed
about the potential hazards of handling contaminated clothing and instructed
about measures to minimize their health risk.
Protective clothing should be kept free of oil and grease and should be
inspected and maintained regularly to preserve its effectiveness.
Protective clothing may interfere with the body's heat dissipation,
especially during hot weather or during work in hot or poorly ventilated work
environments.
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