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 This information may be superseded by new developments in the field of industrial hygiene.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 ETHYL SILICATE
INTRODUCTION
This guideline summarizes pertinent information about ethyl silicate 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Recommendations may be superseded by new developments in these fields;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
C(8)H(20)O(4)Si
* Structure
(For Structure, see paper copy)
* Synonyms
Ethyl silicate, condensed; silicon ethoxide; tetraethoxysilane;
tetraethyl orthosilicate; tetraethyl ester orthosilicic acid;
tetraethyl silicate; ethyl orthosilicate tetraethoxysilane
* Identifiers
1. CAS No.: 78-10-4
2. RTECS No.: VV9450000
3. DOT UN: 1292 29
4. DOT label: Flammable Liquid
* Appearance and odor
Ethyl silicate is a flammable, colorless liquid with a mild, sweet,
alcohol-like odor. An air odor threshold of 17 parts per million (ppm) parts
of air has been reported.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 208.3
2. Boiling point (at 760 mm Hg): 168 degrees C (334 degrees F)
3. Specific gravity (water = 1): 0.94 at 20 degrees C (68 degrees F)
4. Vapor density: 7.2
5. Melting point: -77 degrees C (-106 degrees F)
6. Vapor pressure at 20 degrees C (68 degrees F): 1 mm Hg
7. Solubility: Practically insoluble in water; soluble in alcohol;
slightly soluble in benzene.
8. Evaporation rate: Data not available.
* Reactivity
1. Conditions contributing to instability: Heat, sparks, or flames.
2. Incompatibilities: Contact between ethyl silicate and strong
oxidizers, water, mineral acids, and alkalies should be avoided.
3. Hazardous decomposition products: Toxic gases and vapors (such as
carbon dioxide, silicon dioxide, and carbon monoxide) may be released in a
fire involving ethyl silicate.
4. Special precautions: None reported.
* Flammability
The National Fire Protection Association has assigned a flammability
rating of 2 (moderate fire hazard) to ethyl silicate.
1. Flash point: 51.7 degrees C (125 degrees F) (open cup)
2. Autoignition temperature: Data not available.
3. Flammable limits in air (percent by volume): Lower, 1.3; upper, 23
4. Extinguishant: For small fires use dry chemical, carbon dioxide, water
spray, or standard foam. Use water spray, fog, or standard foam to fight
large fires involving ethyl silicate.
Fires involving ethyl silicate 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. 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
ethyl silicate 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. Do not get water inside the containers. 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 ethyl
silicate.
EXPOSURE LIMITS
* OSHA PEL
The current Occupational Safety and Health Administration (OSHA)
permissible exposure limit (PEL) for ethyl silicate is 100 ppm (850
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 ethyl silicate of 10
ppm (85 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 ethyl silicate a threshold limit value (TLV) of 10 ppm
(85 mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour workweek
[ACGIH 1994, p. 21].
* Rationale for Limits
The NIOSH limit is based on the risk of eye and nose irritation;
lung, liver, and kidney damage in animals [NIOSH 1992].
The ACGIH limit is based on the risk of irritation and on the
effects noted in animals [ACGIH 1991, p. 640].
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to ethyl silicate can occur through inhalation, ingestion,
and eye or skin contact [Sittig 1991, p. 793].
* Summary of toxicology
1. Effects on Animals: Ethyl silicate is an eye, mucous membrane, and
respiratory irritant, a liver and kidney toxin, and a cerebral nervous system
depressant. Acute inhalation exposure also causes profound anemia in animals
[Hathaway et al. 1991]. The lowest lethal inhalation dose is 1,000 ppm for 4
hours and 700 ppm for 6 hours in rats and guinea pigs, respectively [NIOSH
1991]. The oral LD(50) in rats is 6,270 mg/kg; and the dermal LD(50) in
rabbits is 5,878 mg/kg [NIOSH 1991]. Exposure of guinea pigs to 2,530 ppm of
ethyl silicate for 4 hours produced irritation of the eyes and nose,
lacrimation, respiratory difficulty, tremor, narcosis, and death. A
postmortem examination of these animals revealed delayed but profound anemia,
pulmonary edema, acute nephritis, and liver injury [NLM 1992]. Exposure to
400 ppm ethyl silicate for 7 hours a day for 30 days caused significant
mortality in rats. The surviving animals developed kidney, liver, and lung
damage [Hathaway et al. 1991]. In a group of rats, guinea pigs, and mice
exposed to 88, 50, and 23 ppm respectively, for 7 hours a day, 5 days a week,
for 90 days, only the mice exposed to 88 ppm demonstrated a decrease in
kidney weight [ACGIH 1991]. Rats exposed three times to 500 ppm ethyl
silicate for 7 hours developed pronounced kidney damage and slight lung
irritation [NLM 1992]. Rats exposed 5 to 10 times to 125 ppm for 7 hours
developed slight to moderate kidney damage that did not progress after 20
additional exposures [Hathaway et al. 1991]. Liquid ethyl silicate applied
to the eye produces an immediate but transitory irritation that resolves
within 24 hours, and exposure to ethyl silicate vapor in concentrations of
2,500 ppm for 2 hours caused opacification of the cornea in guinea pigs
[Grant 1986].
2. Effects on Humans: Ethyl silicate is an eye, mucous membrane, and
respiratory irritant in humans. By analogy with effects seen in animals, it
may also cause liver and kidney damage, central nervous system depression,
and anemia. At concentrations of 3,000 ppm, ethyl silicate causes extreme
and intolerable irritation of the eyes and mucous membranes; at 1,200 ppm, it
produces tearing of the eyes; at 700 ppm, it causes mild stinging of the eyes
and nose; and at 250 ppm, it produces slight irritation of the eyes and nose
[Hathaway et al. 1991].
* Signs and symptoms of exposure
1. Acute exposure: Signs and symptoms of acute exposure to ethyl silicate
may include stinging of the eyes and nose, tearing of the eyes, respiratory
difficulty, tremor, fatigue, narcosis, nausea and vomiting, signs of liver
and kidney damage, and anemia. Eye contact with the liquid may produce
tearing and irritation, and skin contact may produce drying, cracking, and
inflammation [Sittig 1991].
2. Chronic exposure: Prolonged or repeated skin contact with liquid ethyl
silicate may produce dermatitis [Genium 1989].
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 ethyl silicate and lead to worker
exposures to this substance:
* The manufacture and transportation of ethyl silicate * Use as a
bonding agent for industrial buildings and investment castings, ceramic
shells, crucibles, refractory bricks, and other molded objects * Use as a
protective coating for heat- and chemical-resistant paints, lacquers, and
films * Use in manufacture of protective and preservative coatings for
protection from corrosion (primarily as a binder for zinc dust paints),
chemicals, heat, scratches, and fire * Use in the production of silicones;
as a chemical intermediate in the preparation of soluble silica; as a gelling
agent in organic liquids, as a coating agent inside electric lamp bulbs, and
in the synthesis of fused quartz * Use in textile industry in aqueous
emulsions, deluster, and fireproofing; as a component of lubricants; as a
mold-release agent; and as a heat-resistant adhesive
Methods that are effective in controlling worker exposures to ethyl
silicate, 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 ethyl silicate 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
ethyl silicate, 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 system, liver, kidneys, and blood. 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 ethyl silicate 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 system, liver, kidneys,
and blood.
* 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 ethyl silicate exposure. The interviews,
examinations, and medical screening tests should focus on identifying the
adverse effects of ethyl silicate on the respiratory system, liver, kidneys,
or blood. 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 ethyl silicate.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne ethyl silicate is made
using an XAD-2 tube (100/50 mg sections, 20/50 mesh). Samples are collected
at a maximum flow rate of 0.05 liter/minute until a maximum collection volume
of 9 liters is reached. The sample is then treated with carbon disulfide.
Analysis is conducted by gas chromatography using a flame ionization detector
(GC/FID). This method is fully validated and is described in the OSHA
Computerized Information System [OSHA 1994].
PERSONAL HYGIENE PROCEDURES
If ethyl silicate contacts the skin, workers should flush the affected areas
immediately with plenty of water, followed by washing with soap and water.
Clothing contaminated with ethyl silicate should be removed immediately, and
provisions should be made for the safe removal of the chemical from the
clothing. Persons laundering the clothes should be informed of the hazardous
properties of ethyl silicate.
A worker who handles ethyl silicate should thoroughly wash hands, forearms,
and face with soap and water before eating, using tobacco products, using
toilet facilities, applying cosmetics, or taking medication.
Workers should not eat, drink, use tobacco products, apply cosmetics, or
take medication in areas where ethyl silicate or a solution containing ethyl
silicate is handled, processed, or stored.
STORAGE
Ethyl silicate 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 ethyl silicate
should be protected from physical damage and should be stored separately from
strong oxidizers, water, mineral acids, and alkalies.
SPILLS AND LEAKS
In the event of a spill or leak involving ethyl silicate, 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. Do not touch the spilled material; stop the leak if it is possible to
do so without risk.
5. Use non-sparking tools.
6. Water spray may be used to reduce vapors, but the spray may not prevent
ignition in closed spaces.
7. Keep ethyl silicate out of a confined a space, such as a sewer, because
of the possibility of an explosion, unless the sewer is designed to prevent
the build-up of explosive concentrations.
8. For small liquid spills, take up with sand or other noncombustible
absorbent material and place into closed containers for later disposal.
9. For large liquid spills, build dikes far ahead of the spill to contain
the ethyl silicate for later reclamation or disposal.
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
Ethyl silicate is not subject to EPA emergency planning requirements
under the Superfund Amendments and Reauthorization Act (SARA) (Title III) in
42 USC 11022.
* 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].
Employers are not required by the emergency release notification
provisions in 40 CFR Part 355.40 to notify the National Response Center of an
accidental release of ethyl silicate; there is no reportable quantity for
this substance.
* 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
ethyl silicate 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 ethyl silicate 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 ethyl silicate 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 ethyl silicate. 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 ethyl silicate. There are no published reports on the resistance
of various materials to permeation by ethyl silicate.
To evaluate the use of PPE materials with ethyl silicate, 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 ethyl silicate.
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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